Oligosaccharide compositions and methods for producing thereof

Abstract

To provide an improved method for producing oligosaccharides in a commercially achievable scale, and an oligosaccharide composition.SOLUTION: A method for producing an oligosaccharide composition includes the steps of: a) combining one or more kinds of saccharides and catalyst to produce a first product mixture, in which the first product mixture contains a first oligosaccharide composition and residual catalyst; b) isolating at least a part of residual catalyst from the product mixture; and c) combining further one or more kinds of saccharides and isolated residual catalyst to further produce a product mixture, where the further product mixture contains a further oligosaccharide composition, catalytic activity of the isolated residual catalyst in production of the further oligosaccharide composition is at least 30% of the catalytic activity of catalyst in production of the first oligosaccharide composition.SELECTED DRAWING: None

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims the benefit of U.S. Provisional Patent Application No. 62 / 022,579, filed Jul. 9, 2014, and U.S. Provisional Patent Application No. 62 / 108,035, filed Jan. 26, 2015, which are hereby incorporated by reference in their entirety.

[0002] The present disclosure generally relates to oligosaccharide compositions and methods of producing such oligosaccharide compositions, and more particularly to methods of using a catalyst having acidic and ionic groups to polymerize sugars such as glucose and galactose to produce an oligosaccharide composition.

Background Art

[0003] The condensation of sugars to soluble oligosaccharides has important economic, nutritional and therapeutic relevance. It is well known that the excessive consumption of sugars by humans and animals is associated with various negative health symptoms such as obesity and diabetes. It has been further established that a diet rich in fibers such as indigestible oligosaccharides and polysaccharides promotes health and a good state of life. Some dietary fibers interact favorably with the ecosystem of the microbiota in the human and animal gut, stimulating the growth of beneficial gut bacteria, inhibiting the growth of undesirable gut bacteria, and inhibiting the ability of pathogenic bacteria to colonize the gut.

[0004] Oligosaccharides can be added to foods to impart desirable flavors, mouthfeel and viscosities. Further, oligosaccharides that are not digested by humans provide little or no calorie value to foods. There is significant commercial interest in replacing some of the raw sugar components in foods with oligosaccharides to reduce the calorie content of such foods and improve their effect on the human microbiota. There is interest in incorporating oligosaccharide components to reduce the sugar content and increase the dietary fiber content of breakfast cereals, granolas and other types of bars, yogurts, ice creams, breads, cake mixes, and nutritional shakes and supplements.

[0005] There is further interest in incorporating oligosaccharide components into animal feed to improve the quality of that nutrition. Oligosaccharides can be added to animal feed to improve gut health, increase weight gain, and promote feed efficiency. Additionally, oligosaccharides that are not digested by the animal can pass through the stomach and upper digestive system and be fermented by the microorganisms in the gut. There is commercial interest in incorporating oligosaccharides into the feed of poultry, swine, aquaculture, and ruminant animals to improve the animal's microbiota.

[0006] For the purpose of achieving objectives related to improving human and animal nutrition and health, oligosaccharides having specific structures, or a range of structural characteristics, are desirable. However, currently, such oligosaccharides are limited to those obtained from sources such as corn meal, yeast solids, dairy products, inulin, gums (such as guar gum or acacia gum), pectin, hemicellulose extracts, and other such agricultural and industrial food products. In other examples, oligosaccharides are produced by the fermentation, roasting, and polymerization of glucose in the presence of aqueous acid of starch and grains. Oligosaccharides of the type obtained by biological production are limited in terms of the diversity of chemical structures that can be produced, the high cost of industrial fermentation, and the complex purification methods required to remove salts, buffers, and other fermentation by-products to make the oligosaccharides suitable for human consumption.

[0007] Methods known in the art are limited in terms of the diversity of oligosaccharide structures that can be produced and often have additional high-cost production steps. These can include the neutralization and / or removal of aqueous acid or its salts, the decolorization of the product to a suitable level, and the isolation and disposal of spent catalysts that cannot be reused. Summary of the Invention Problems to be Solved by the Invention

[0008] Therefore, there is an ongoing need for improved methods of producing oligosaccharides on a commercially feasible scale. Means for Solving the Problems

[0009] The present disclosure addresses the above need by providing a method for producing an oligosaccharide composition and a functionalized oligosaccharide composition using a catalyst comprising a polymer catalyst and a solid-supported catalyst having an acidic group and an ionic group. Specifically, the catalysts described herein can be used to polymerize sugars such as glucose, galactose, lactose, xylose, maltose, mannose, etc. to produce oligosaccharide compositions desirable for various applications, including nutritional and therapeutic uses in humans in animals. The catalysts described herein can also be used to produce a functionalized oligosaccharide composition, wherein one or more oligosaccharides of the composition are attached to one or more pendant functional groups and / or crosslinkable functional groups. Due to the polymeric nature or the nature of being supported on a solid of the catalyst, this catalyst can be easily removed from the produced oligosaccharide composition.

[0010] In one aspect, there is provided a method for producing an oligosaccharide composition by combining one or more sugars and a catalyst to produce the oligosaccharide composition.

[0011] In another aspect, there is provided a method for producing an oligosaccharide composition by combining one or more sugars and a catalyst to produce a first product mixture, the first product mixture comprising a first oligosaccharide composition and a residual catalyst, isolating at least a portion of the residual catalyst from the first product mixture, and combining one or more additional sugars and the isolated residual catalyst to produce a further product mixture, the further product mixture comprising a further oligosaccharide composition.

[0012] In one variation, the catalytic activity of the isolated residual catalyst in the production of the further oligosaccharide composition is at least 30% of the catalytic activity of the catalyst in the production of the first oligosaccharide composition. In other variations, the molar selectivity of the first oligosaccharide composition is at least 70%, at least 80%, at least 85%, at least 86%, at least 87%, at least 88%, at least 89%, at least 90%, at least 95%, or at least 99%. In yet other variations, the molar selectivity of the further oligosaccharide composition is at least 70%, at least 80%, at least 85%, at least 86%, at least 87%, at least 88%, at least 89%, at least 90%, at least 95%, or at least 99%.

[0013] In another aspect, provided herein is a method for producing an oligosaccharide composition, the method comprising combining one or more sugars and a catalyst to produce an oligosaccharide composition, wherein the molar selectivity of the oligosaccharide composition is at least 70%, at least 80%, at least 85%, at least 86%, at least 87%, at least 88%, at least 89%, at least 90%, at least 95%, or at least 99%.

[0014] In some variations, the present oligosaccharide composition is further combined with one or more functionalized compounds to produce a functionalized oligosaccharide composition, wherein the one or more functionalized compounds are independently selected from the group consisting of carboxylic acids, sugar alcohols, amino acids, amino sugars, alcohols, sulfates, and phosphates.

[0015] In yet another aspect, a method for producing a functionalized oligosaccharide composition, the method comprising combining one or more sugars, a catalyst, and one or more functionalized compounds, wherein the one or more functionalized compounds are independently selected from the group consisting of carboxylic acids, sugar alcohols, amino acids, amino sugars, alcohols, sulfates, and phosphates.

[0016] In yet another aspect, there is provided a step of combining a feedstock sugar and a catalyst to form a reaction mixture, wherein the feedstock sugar contains an α-1,4 bond, and a step of converting at least a part of the α-1,4 bonds in the feedstock sugar into one or more non-α-1,4 bonds to produce an oligosaccharide composition from at least a part of the reaction mixture. In some embodiments, the non-α-1,4 bond is selected from the group consisting of an α-1,2 bond, a β-1,2 bond, an α-1,3 bond, a β-1,3 bond, a β-1,4 bond, an α-1,6 bond, and a β-1,6 bond. In one embodiment, the non-α-1,4 bond is selected from the group consisting of a β-1,4 bond, an α-1,3 bond, a β-1,3 bond, an α-1,6 bond, and a β-1,6 bond.

[0017] In yet another aspect, there is provided a step of contacting an α-1,4 polysaccharide with a catalyst, wherein the catalyst comprises an acidic monomer and an ionic monomer linked to form a polymer backbone, or the catalyst comprises a solid support, an acidic site bonded to the solid support, and an ionic site bonded to the solid support, and a step of converting at least a part of the α-1,4 bonds in the α-1,4 polysaccharide into one or more non-α-1,4 bonds selected from the group consisting of an α-1,2 bond, a β-1,2 bond, an α-1,3 bond, a β-1,3 bond, a β-1,4 bond, an α-1,6 bond, and a β-1,6 bond to produce a polysaccharide having a mixture of linkages from at least a part of the α-1,4 polysaccharide There is provided a method for converting an α-1,4 polysaccharide into a polysaccharide having a mixture of linkages. In some variations, the one or more non-α-1,4 bonds are selected from the group consisting of a β-1,4 bond, an α-1,3 bond, a β-1,3 bond, an α-1,6 bond, and a β-1,6 bond.

[0018] In some embodiments of the above aspects, the catalyst is a polymer catalyst comprising an acidic monomer and an ionic monomer linked to form a polymer backbone, or the catalyst is a solid-supported catalyst comprising a solid support, an acidic site bonded to the solid support, and an ionic site bonded to the solid support.

[0019] In another aspect, the oligosaccharide or oligosaccharide composition is obtained by any one of the methods described herein. In some embodiments of the oligosaccharide composition, the monosaccharide monomers are linked by glycosidic bonds to form an oligomer backbone, which is optionally substituted by one or more pendant functional groups, one or more crosslinkable functional groups, or a combination thereof.

[0020] In some embodiments of the above aspects, the oligosaccharide composition comprises monosaccharide monomers linked by glycosidic bonds, wherein the monosaccharide monomers are independently selected from the group consisting of C5 monosaccharides and C6 monosaccharides, each glycosidic bond is independently selected from the group consisting of α-1,4 bonds, α-1,2 bonds, β-1,2 bonds, α-1,3 bonds, β-1,3 bonds, β-1,4 bonds, α-1,6 bonds, and α-1,6 bonds, at least 10% of the oligosaccharide composition has a degree of polymerization of at least 3, and at least a portion of the oligosaccharide composition contains monosaccharide monomers that contain at least two different glycosidic bonds.

[0021] In another aspect, provided herein is the use of any one of a catalyst comprising a polymer catalyst and a solid-supported catalyst, the catalyst comprising a plurality of acidic groups and a plurality of cationic groups, for preparing an oligosaccharide composition from one or more sugars.

[0022] The following description illustrates exemplary compositions, methods, parameters, etc. However, it should be recognized that such description is not intended as a limitation on the scope of the present disclosure, but rather is provided as a description of exemplary embodiments.

Brief Description of the Drawings

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DETAILED DESCRIPTION OF THE INVENTION

[0024] The following description explains exemplary methods, parameters, etc. However, it should be recognized that such description is not intended as a limitation on the scope of the present disclosure, but rather is provided as a description of exemplary embodiments.

[0025] In some embodiments, catalysts are described herein that can be used to produce an oligosaccharide composition comprising a functionalized oligosaccharide composition from one or more sugars, such as monosaccharides like glucose and galactose. Such catalysts can be polymer catalysts or solid-supported catalysts.

[0026] Unlike methods that use conventional catalysts known in the art (e.g., soluble acids, solid acid catalysts (such as zeolites, clays or ion exchange resins) or soluble acidic polymers) to produce oligosaccharides and functionalized oligosaccharides, the methods using the catalysts described herein achieve efficient production of oligosaccharides and easy catalyst recycling and reuse. The ability to recycle and reuse the catalyst provides several advantages, including cost reduction in oligosaccharide production. Unlike conventional catalysts, the catalysts used in the methods described herein contain both acidic monomers and cationic monomers, and these monomers act to attract and / or stabilize the sugar reactants, resulting in improved selectivity (yield) to give higher yields, particularly of oligosaccharide products, and reducing sugar degradation to a lower level. The catalysts used in the methods described herein are less corrosive, easier to handle compared to conventional catalysts, and of course, phase-separate from the aqueous product and can thus be easily recovered. Accordingly, a stable and reusable catalyst is provided herein that can efficiently produce oligosaccharide materials on a commercially feasible scale.

[0027] Referring to FIG. 1, method 100 illustrates an exemplary method for producing an oligosaccharide composition from sugars, and the oligosaccharide composition thus produced can subsequently be refined and further processed to form food ingredients such as oligosaccharide syrups or powders. In step 102, one or more sugars are combined with a catalyst in a reactor. The sugars can include, for example, monosaccharides, disaccharides and / or trisaccharides. The catalyst has both acidic groups and ionic groups. In some variations, the catalyst is a polymeric catalyst comprising acidic monomers and ionic monomers. In other variations, the catalyst is a solid-supported catalyst comprising acidic sites and ionic sites.

[0028] In step 104, the oligosaccharide composition in step 102 is refined to remove fine solids, reduce color, reduce conductivity, and / or modify the molecular weight distribution. For example, any suitable method known in the art for refining an oligosaccharide composition can be used, including the use of a filtration unit, carbon or other absorbent, chromatography separator, or ion exchange column. For example, in one variation, the present oligosaccharide composition is treated with powdered activated carbon to reduce color, microfiltered to remove fine solids, and passed through a strongly acidic cation exchange resin and a weakly basic anion exchange resin to remove salts. In another variation, the oligosaccharide composition is microfiltered to remove fine solids and passed through a weakly basic anion exchange resin. In yet another variation, the oligosaccharide composition is passed through a simulated moving bed chromatography separator to remove low molecular weight species.

[0029] In step 106, further processing is performed on the refined oligosaccharide composition to produce either an oligosaccharide syrup or powder. For example, in one variation, the refined oligosaccharide is concentrated to form a syrup. Any suitable method known in the art for concentrating a solution, such as the use of a vacuum evaporator, can be used. In another variation, the refined oligosaccharide composition is spray dried to form a powder. Any suitable method known in the art for spray drying a solution to form a powder can be used.

[0030] In other variations, method 100 may be modified to add steps. For example, the oligosaccharide composition produced in step 102 may be diluted (e.g., in a dilution tank) and then carbon treated to decolorize the oligosaccharide composition prior to refining in step 104. In other variations, the oligosaccharide composition produced in step 102 may be further processed during a simulated moving bed (SMB) separation step to reduce the digestible carbohydrate content.

[0031] In other variations, method 100 may be modified to have few steps. For example, in one variation, step 106 for producing the oligosaccharide syrup or powder may be omitted, and the refined oligosaccharide composition of step 104 may be used directly as a component to manufacture a food product.

[0032] The catalysts described herein can also be used to produce a functionalized oligosaccharide composition, which is a functionalized oligosaccharide composition, at least a portion of the composition being bonded to one or more pendant functional groups and / or crosslinkable functional groups. Such functionalized oligosaccharide compositions may be produced in one step by combining a sugar and a functionalized compound in the presence of a catalyst, or by combining a sugar and a catalyst to produce an oligosaccharide composition, and then combining the oligosaccharide composition and a functionalized compound in the presence of a catalyst in two steps. Thus, a stable and reusable catalyst is described herein that can efficiently produce functionalized oligosaccharide materials on a commercially feasible scale.

[0033] Referring to FIG. 14, method 200 illustrates an exemplary method for producing a functionalized oligosaccharide composition from a sugar and a functionalized compound. In step 208, one or more sugars 202 are combined in a reactor with a catalyst 204 and one or more functionalized compounds 206. The sugars can include, for example, monosaccharides, disaccharides, and / or trisaccharides. The catalyst has both acidic groups and ionic groups. In some variations, the catalyst is a polymeric catalyst comprising an acidic monomer and an ionic monomer. In other variations, the catalyst is a solid-supported catalyst comprising acidic sites and ionic sites. The functionalized compounds can include, for example, sugar alcohols, carboxylic acids, amino acids, amino sugars, alcohols, and / or sulfates. The functionalized oligosaccharide composition is produced in step 210. It is understood that method 200 may be modified to add steps. For example, in some variations, the functionalized oligosaccharide composition produced in step 210 is refined, concentrated, powdered, and / or decolorized.

[0034] Referring to FIG. 15, method 300 illustrates an exemplary method for generating a functionalized oligosaccharide composition from an oligosaccharide composition and a functionalized compound. In step 306, one or more sugars 302 are combined with a catalyst 304 in a reactor. The sugars can include, for example, monosaccharides, disaccharides, and / or trisaccharides. The catalyst has both acidic groups and ionic groups. In some variations, the catalyst is a polymer catalyst comprising an acidic monomer and an ionic monomer. In other variations, the catalyst is a solid-supported catalyst comprising an acidic site and an ionic site. The oligosaccharide composition is produced in step 310. The functionalized compound 312 is combined with the oligosaccharide composition in step 320. The functionalized compound can include, for example, sugar alcohols, carboxylic acids, amino acids, amino sugars, alcohols, and / or sulfates. The functionalized oligosaccharide composition is produced in step 330. It is understood that method 300 may be modified to add steps. For example, in some variations, the functionalized oligosaccharide composition is refined, concentrated, powdered, and / or decolorized. For example, in some variations, the oligosaccharide composition produced in step 310 is refined, concentrated, powdered, and / or decolorized and then combined with the functionalized compound in step 320. In other variations, the functionalized composition produced in step 330 is refined, concentrated, powdered, and / or decolorized.

[0035] The respective steps in exemplary methods 100, 200, and 300, the reactants and processing conditions in each step, and the compositions produced in each step are described in further detail below.

[0036] Definitions As used herein, "alkyl" includes, when unsubstituted, monovalent straight-chain or branched-chain saturated hydrocarbon groups containing only C and H, and combinations thereof. Examples include methyl, ethyl, propyl, butyl and pentyl. When an alkyl residue having a specific number of carbons is named, it is intended to be described as encompassing all geometric isomers having that number of carbons. Thus, for example, "butyl" is intended to include n-butyl, sec-butyl, iso-butyl and tert-butyl, and "propyl" is intended to include n-propyl and iso-propyl. The total number of carbon atoms in each such group is sometimes described herein. For example, if a group can contain up to 10 carbon atoms, the group can be represented as 1-10C, or as C1-C10 or C1-10. In some embodiments, the alkyl may be substituted. Suitable alkyl substituents can include, for example, hydroxy, amino and halo.

[0037] As used herein, "alkylene" refers to a divalent but otherwise the same residue as alkyl. Examples of alkylene include methylene (-CH 2 -), ethylene (-CH 2 CH 2 -), propylene (-CH 2 CH 2 CH 2 -), butylene (-CH 2 CH 2 CH 2 CH 2 -).

[0038] As used herein, "alkylenecarbamate" refers to an alkylene moiety in which one or more of the methylene units of the alkylene moiety have been replaced by a carbamate moiety (-C(O)-O-NR- or -O-C(O)-NR-, where R can be, for example, alkyl or aryl). In some embodiments, the alkylenecarbamate may be substituted. Suitable alkylenecarbamate substituents can include, for example, hydroxyl, amino and halo.

[0039] As used herein, "alkylene ester" refers to an alkylene moiety in which one or more of the methylene units of the alkylene moiety are replaced by an ester moiety (-C(O)-O- or -O-C(O)-). In some embodiments, the alkylene ester may be substituted and further have one or more substituents. Suitable alkylene ester substituents may include, for example, hydroxyl, amino, and halo.

[0040] As used herein, "alkylene ether" refers to an alkylene moiety in which one or more of the methylene units of the alkylene moiety are replaced by an ether moiety (-C(O)-). In some embodiments, the alkylene ether may be substituted and further have one or more substituents. Suitable alkylene ether substituents may include, for example, hydroxyl, amino, and halo.

[0041] As used herein, "alkenyl" refers to an unsaturated hydrocarbon group having at least one olefinically unsaturated moiety (i.e., having at least one moiety of the formula C=C). Alkenyl, when unsubstituted, contains only C and H. When an alkenyl residue having a specific number of carbons is named, it is intended to be described as encompassing all geometric isomers having that number of carbons. Thus, for example, "butenyl" is intended to include n-butenyl, sec-butenyl, and iso-butenyl. Examples of alkenyl include -CH=CH 2 , -CH 2 -CH=CH 2 and -CH 2 -CH=CH-CH=CH 2 may be included. In some embodiments, the alkenyl may be substituted. Suitable alkenyl substituents may include, for example, hydroxy, amino, and halo.

[0042] As used herein, "alkenylene" refers to a divalent but the same residue as alkenyl. Examples of alkenylene include ethylene (-CH=CH-), propylene (-CH 2-CH=CH-) and butylene (-CH 2 -CH=CH-CH 2 -) is included.

[0043] As used herein, "alkynyl" refers to an unsaturated hydrocarbon group having at least one acetylenic unsaturated moiety (i.e., having at least one moiety of the formula C≡C). Alkynyl, when unsubstituted, contains only C and H. When an alkynyl residue having a specific number of carbons is named, all geometric isomers having that number of carbons are intended to be included and described. Thus, for example, "pentynyl" is intended to include n-pentynyl, sec-pentynyl, iso-pentynyl and tert-pentynyl. Examples of alkynyl include -C≡CH or -C≡C-CH 3 may be included. In some embodiments, alkynyl may be substituted. Suitable alkynyl substituents may include, for example, hydroxy, amino and halo.

[0044] As used herein, "aryl" refers to an unsaturated aromatic carbocyclic group having a monocyclic ring (e.g., phenyl) or a plurality of fused rings (e.g., naphthyl or anthryl) (the fused rings may or may not be aromatic). Aryl, when unsubstituted, contains only C and H. An aryl group having two or more rings, where at least one ring is non-aromatic, can be linked to the parent structure at either an aromatic ring position or a non-aromatic ring position. In one variation, an aryl group having two or more rings, where at least one ring is non-aromatic, is linked to the parent structure at an aromatic ring position. Examples of aryl may include phenyl, phenol and benzyl. In some embodiments, aryl may be substituted. Suitable aryl substituents may include, for example, alkyl, alkenyl, alkynyl, hydroxy, amino and halo.

[0045] As used herein, "arylene" refers to a divalent residue that is the same as aryl.

[0046] As used herein, "cycloalkyl", when unsubstituted, includes a carbocyclic non-aromatic group containing only C and H and linked through ring carbon atoms. A cycloalkyl can consist of one ring such as cyclohexyl, or multiple rings such as adamantyl. A cycloalkyl having two or more rings can be fused, spiro or bridged, or a combination thereof. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl and decahydronaphthalenyl. In some embodiments, the cycloalkyl may be substituted. Suitable cycloalkyl substituents can include, for example, alkyl, hydroxy, amino and halo.

[0047] As used herein, "cycloalkylene" refers to a divalent residue that is the same as cycloalkyl.

[0048] As used herein, "heteroaryl" refers to an unsaturated aromatic carbocyclic group having 1 to 10 carbon atoms forming the ring and at least one heteroatom including, but not limited to, heteroatoms such as nitrogen, oxygen and sulfur. A heteroaryl group can have a single ring (e.g., pyridyl, pyridinyl, imidazolyl) or multiple fused rings (e.g., indolizinyl, benzothienyl) (the fused rings may or may not be aromatic). A heteroaryl group having two or more rings with at least one ring being non-aromatic can be linked to the parent structure at either an aromatic ring position or a non-aromatic ring position. In one variation, a heteroaryl group having two or more rings with at least one ring being non-aromatic is linked to the parent structure at an aromatic ring position. Examples of heteroaryl can include pyridyl, pyridinyl, imidazolyl, and thiazolyl. In some embodiments, the heteroaryl may be substituted. Suitable heteroaryl substituents can include, for example, alkyl, alkenyl, alkynyl, hydroxy, amino and halo.

[0049] As used herein, "heteroarylene" refers to a divalent residue having the same residues as heteroaryl.

[0050] Alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, ether, ester, and carbamate may be substituted, in which case the specific group(s) described may or may not have non-hydrogen substituents, or the group(s) may have one or more non-hydrogen substituents. It is understood that unless otherwise specified, the total number of such substituents that may be present is equal to the number of H atoms present in the unsubstituted form of the group described.

[0051] Method for producing an oligosaccharide composition In one aspect, a method is described herein for producing an oligosaccharide composition comprising a functionalized oligosaccharide composition from one or more sugars using a catalyst comprising a polymer catalyst and a solid-supported catalyst. The one or more sugars can be any suitable sugar, such as a C5 or C6 monosaccharide, as detailed below. As used herein, "oligosaccharide" refers to a compound containing two or more monosaccharide units linked by glycosidic bonds.

[0052] In one aspect, provided herein is a method for producing one or more oligosaccharides, comprising forming a reaction mixture for producing one or more oligosaccharides by combining one or more sugars with a polymer catalyst having a plurality of acidic monomers and a plurality of cationic monomers.

[0053] In another aspect, provided herein is a method for producing one or more oligosaccharides, comprising forming a reaction mixture for producing one or more oligosaccharides by combining one or more sugars with a solid-supported catalyst having a solid support, a plurality of acidic sites bonded to the solid support, and a plurality of ionic sites bonded to the solid support.

[0054] Sugar reactant One or more sugars of the methods described herein can include any suitable sugars capable of producing one or more corresponding oligosaccharides. In some embodiments, the one or more sugars are selected from monosaccharides, disaccharides, trisaccharides, and short-chain oligosaccharides, or any mixture thereof. In certain embodiments, the one or more sugars are one or more monosaccharides, disaccharides, and / or trisaccharides. In some embodiments, the one or more sugars are one or more monosaccharides, such as one or more C5 or C6 monosaccharides. Exemplary monosaccharides include glucose, galactose, mannose, fructose, xylose, xylulose, arabinose, and the like. In some embodiments, the one or more sugars are one or more C5 monosaccharides. In other embodiments, the one or more sugars are one or more C6 monosaccharides. In still other embodiments, the one or more sugars are one or more C3 monosaccharides. In some embodiments, the one or more sugars are selected from glucose, galactose, ribose, allose, glyceraldehyde, and mannose. In other embodiments, the one or more sugars are selected from fructose, xylose, and arabinose. In some embodiments, the one or more sugars include one or more disaccharides. Exemplary disaccharides include lactose, maltose, sucrose, cellobiose, and the like. In some embodiments, the one or more sugars include one or more trisaccharides, such as raffinose. In certain embodiments, the one or more sugars include one or more deoxysugars, such as fucose and rhamnose. In some embodiments, the one or more sugars include a mixture of short-chain oligosaccharides, such as maltodextrin. In certain embodiments, the one or more sugars are corn syrup obtained from partial hydrolysis of corn starch. In a particular embodiment, the one or more sugars are corn syrup having a dextrose equivalent (DE) of less than 50 (e.g., 10 DE corn syrup, 18 DE corn syrup, 25 DE corn syrup, or 30 DE corn syrup).

[0055] In some embodiments, the one or more sugars are selected from glucose, galactose, xylose, arabinose, fructose, mannose, fucose, lactose, maltose, ribose, allose, glyceraldehyde, and rhamnose.

[0056] In some embodiments, the method includes combining two or more sugars and a polymeric catalyst to produce one or more oligosaccharides. In some embodiments, the two or more sugars are selected from glucose, galactose, mannose, and lactose (e.g., glucose and galactose).

[0057] In other embodiments, the method includes combining a mixture of sugars (e.g., monosaccharides, disaccharides, trisaccharides, etc., and / or other short-chain oligosaccharides) and a polymeric catalyst to produce one or more oligosaccharides. In certain embodiments, the method includes combining corn glucose syrup and a polymeric catalyst to produce one or more oligosaccharides.

[0058] In other embodiments, the method includes combining a polysaccharide and a polymeric catalyst to produce one or more oligosaccharides. In some embodiments, the polysaccharide is selected from starch, guar gum, xanthan gum, and acacia gum.

[0059] Functionalized oligosaccharide composition In some variations, the oligosaccharide compositions described herein are functionalized oligosaccharide compositions. The functionalized oligosaccharide compositions can be produced by combining one or more sugars with one or more functionalized compounds in the presence of a catalyst, by combining an oligosaccharide composition with one or more functionalized compounds in the presence of a catalyst, or by combining one or more sugars, an oligosaccharide composition, and one or more functionalized compounds in the presence of a catalyst. Thus, in one aspect, provided herein is a method for producing a functionalized oligosaccharide from a mixture of one or more sugars, an oligosaccharide composition or a combination thereof, and one or more functionalized compounds, using a catalyst including a polymer catalyst and a solid-supported catalyst as described herein. The one or more sugars can be any suitable sugar such as a C5, C6 or C3 monosaccharide as described herein. As used herein, "functionalized oligosaccharide" refers to a compound containing two or more monosaccharide units linked by a glycosidic bond, wherein one or more hydroxyl groups in the monosaccharide units are independently replaced by a functionalized compound or include a linkage to a functionalized compound. The functionalized compound can be bonded to the oligosaccharide via an ether, ester, oxygen-sulfur, amine or oxygen-phosphorus bond and can be a compound that does not contain a monosaccharide unit.

[0060] Functionalized compound In certain variations, the functionalized compound includes one or more functional groups independently selected from amines, hydroxyls, carboxylic acids, sulfur trioxide, sulfates and phosphates. In some variations, the one or more functionalized compounds are independently selected from the group consisting of amines, alcohols, carboxylic acids, sulfates, phosphates or sulfur oxides.

[0061] In some variations, the functionalized compound has one or more hydroxyl groups. In some variations, the functionalized compound having one or more hydroxyl groups is an alcohol. Such alcohols can include, for example, alkanols and sugar alcohols.

[0062] In certain variations, the functionalized compound is an alkanol having one hydroxyl group. For example, in some variations, the functionalized compound is selected from ethanol, propanol, butanol, pentanol, and hexanol. In other variations, the functionalized compound has two or more hydroxyl groups. For example, in some variations, the functionalized compound is selected from propanediol, butanediol, and pentanediol.

[0063] In other embodiments, the method includes combining a mixture of a sugar and a sugar alcohol with a polymer catalyst to produce a functionalized oligosaccharide composition. In certain embodiments, the method includes combining one or more sugars and one or more alcohols selected from the group consisting of glucitol, sorbitol, xylitol, lactitol, and arabinitol with a polymer catalyst to produce a functionalized oligosaccharide composition. In certain variations, the functionalized compound is a sugar alcohol. For example, in some variations, the functionalized compound is sorbitol, xylitol, arabitol, glycerol, erythritol, mannitol, galacitol, fucitol, iditol, inositol, volemitol, or lactitol, or any combination thereof.

[0064] In certain variations where the functionalized compound contains a hydroxyl group, the functionalized compound may become attached to the monosaccharide unit via an ether bond. The oxygen of the ether bond may be derived from the monosaccharide unit or the functionalized compound.

[0065] In other variations, the functionalized compound contains one or more carboxylic acid functional groups. For example, in some variations, the functionalized compound is selected from lactic acid, acetic acid, citric acid, pyruvic acid, succinic acid, glutamic acid, itaconic acid, malic acid, maleic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, adipic acid, isobutyric acid, formic acid, levulinic acid, valeric acid, and isovaleric acid. In other variations, the functionalized compound is a sugar acid. For example, in one embodiment, this functionalized compound is gluconic acid. In certain variations where the functionalized compound contains a carboxylic acid group, the functionalized compound may become bonded to the monosaccharide unit via an ester bond. The non-carbonyl oxygen of the ester bond may be derived from the monosaccharide unit or the functionalized compound.

[0066] In still other variations, the functionalized compound contains one or more amine groups. For example, in some variations, the functionalized compound is an amino acid, while in another variation, the functionalized compound is an amino sugar. In one variation, the functionalized compound is selected from glutamic acid, aspartic acid, glucosamine, and galactosamine. In certain variations where the functionalized compound contains an amine group, the functionalized compound may become bonded to the monosaccharide unit via an amine bond.

[0067] In yet another variation, the functionalized compound contains a sulfur trioxide group or a sulfate group. For example, in one variation, the functionalized compound is a dimethylformamide sulfur trioxide complex. In another variation, the functionalized compound is sulfate. In one embodiment, the sulfate is generated in situ, for example, from sulfur trioxide. In certain variations where the functionalized compound contains sulfur trioxide or a sulfate group, the functionalized compound may become bonded to the monosaccharide unit via an oxygen-sulfur bond.

[0068] In still other variations, the functionalized compound contains a phosphate group. In certain variations where the functionalized compound contains a phosphate group, the functionalized compound may become bonded to the monosaccharide unit via an oxygen-phosphorus bond.

[0069] It is to be understood that the functionalized compounds described herein can contain combinations of functional groups. For example, the functionalized compound may include one or more hydroxyl groups and one or more amine groups (e.g., amino sugars). In other embodiments, the functionalized compound may include one or more hydroxyl groups and one or more carboxylic acid groups (e.g., sugar acids). In still other embodiments, the functionalized compound may include one or more amine groups and one or more carboxylic acid groups (e.g., amino acids). In still other embodiments, the functionalized compound includes one or more additional functional groups such as esters, amides, and / or ethers. For example, in certain embodiments, the functionalized compound is sialic acid (e.g., N-acetylneuraminic acid, 2-keto-3-deoxynononic acid, and other N- or O-substituted derivatives of neuraminic acid).

[0070] It is further to be understood that the functionalized compound can belong to one or more of the above groups. For example, glutamic acid is both an amine and a carboxylic acid, and gluconic acid is both a carboxylic acid and an alcohol.

[0071] In some variations, the functionalized compound forms a pendant group on the oligosaccharide. In other variations, the functionalized compound forms a crosslinking group between an oligomer backbone and a second oligomer backbone, where each oligomer backbone independently includes two or more monosaccharide units linked by glycosidic bonds, and the functionalized compound is bonded to both backbones. In other variations, the functionalized compound forms a crosslinking group between an oligomer backbone and a monosaccharide, where the oligomer backbone includes two or more monosaccharide units linked by glycosidic bonds, and the functionalized compound is bonded to the backbone and the monosaccharide.

[0072] Pendant functional group In certain variations, a functionalized oligosaccharide composition is produced by combining one or more sugars and one or more functionalized compounds in the presence of a catalyst comprising a polymer catalyst and a solid-supported catalyst as described herein. In certain embodiments, the functionalized compound is attached to a subunit of the monosaccharide as a pendant functional group.

[0073] The pendant functional group can include a functionalized compound that is attached to one monosaccharide unit and not attached to any other monosaccharide units. In some variations, the pendant functional group is a single functionalized compound attached to one monosaccharide unit. For example, in one variation, the functionalized compound is acetic acid and the pendant functional group is an acetate attached to the monosaccharide via an ester linkage group. In another variation, the functionalized compound is propionic acid and the pendant functional group is a propionate attached to the monosaccharide via an ester linkage group. In yet another variation, the functionalized compound is butanoic acid and the pendant functional group is a butanoate attached to the monosaccharide via an ester linkage group. In other variations, the pendant functional group is formed from linking together a plurality of functionalized compounds. For example, in some embodiments, the functionalized compound is glutamic acid and the pendant functional group is a peptide chain of two, three, four, five, six, seven, or eight glutamic acid residues, where in this case the chain is attached to the monosaccharide via an ester linkage group. In other embodiments, the peptide chain is attached to the monosaccharide via an amine linkage group.

[0074] The pendant functional group can include a single linking group to the monosaccharide, or a plurality of linking groups to the monosaccharide. For example, in one embodiment, the functionalized compound is ethanediol and the pendant functional group is an ethyl attached to the monosaccharide via two ether linkage groups.

[0075] Referring to FIG. 16, method 400 illustrates an exemplary scheme for generating oligosaccharides containing various pendant functional groups. In method 400, monosaccharide 402 (represented by symbols) is combined with ethanediol 404, which is a functionalized compound, in the presence of catalyst 406 to produce an oligosaccharide. A portion 410 of the oligosaccharide is shown in FIG. 16, where the monosaccharides linked by glycosidic bonds are represented by symbols with circles and lines. The oligosaccharide contains three different pendant functional groups as indicated by the labeled regions. These pendant functional groups include a single functionalized compound bonded to a single monosaccharide unit via one linking group, two functionalized compounds linked together to form a pendant functional group (this pendant functional group is linked to a single monosaccharide unit via one linking group), and a single functionalized compound bonded to a single monosaccharide unit via two linking groups. Although the functionalized compound used in method 400 is ethanediol, it is understood that any of the functionalized compounds described herein or combinations thereof may be used. Although multiple pendant functional groups are present in portion 410 of the oligosaccharide, it is further understood that the number and type of pendant functional groups may be varied in other variations of method 400.

[0076] It is understood that any functionalized compound can form a pendant functional group. In some variations, the functionalized oligosaccharide composition contains one or more pendant groups selected from the group consisting of glucosamine, galactosamine, citric acid, succinic acid, glutamic acid, aspartic acid, glucuronic acid, butyric acid, itaconic acid, malic acid, maleic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, adipic acid, isobutyric acid, formic acid, levulinic acid, valeric acid, isovaleric acid, sorbitol, xylitol, arabinitol, glycerol, erythritol, mannitol, galactitol, fucitol, iditol, inositol, volemitol, lactitol, ethanol, propanol, butanol, pentanol, hexanol, propanediol, butanediol, pentanediol, sulfate, and phosphate.

[0077] Crosslinkable functional group In certain variations, a functionalized oligosaccharide containing a crosslinkable functional group is produced by combining one or more sugars and one or more functionalized compounds in the presence of a catalyst, including a polymer catalyst and a solid-supported catalyst, as described herein.

[0078] The crosslinkable functional group can include a functionalized compound that is attached to one monosaccharide unit and is attached to at least one additional monosaccharide unit. The monosaccharide units can independently be a monosaccharide unit of the same oligosaccharide backbone, a monosaccharide unit of a different oligosaccharide backbone, or a sugar of a monosaccharide that is not attached to any additional monosaccharides. In some variations, the crosslinkable functional compound is attached to one additional monosaccharide unit. In other variations, the crosslinkable functional compound is attached to two or more additional monosaccharide units. For example, in some embodiments, the crosslinkable functional compound is attached to 2, 3, 4, 5, 6, 7, or 8 additional monosaccharide units. In some variations, the crosslinkable functional group is formed by linking a single functionalized compound to two monosaccharide units. For example, in one embodiment, the functionalized compound is glutamic acid, and the crosslinkable functional group is a glutamate residue that is attached to one monosaccharide unit via an ester bond and to an additional monosaccharide unit via an amine bond. In other embodiments, the crosslinkable functionalized group is formed by linking multiple functionalized compound molecules to each other. For example, in one embodiment, the functionalized compound is ethanediol, and the crosslinkable functional group is a linear oligomer of four ethanediol molecules that are attached to each other via ether bonds, wherein the first ethanediol molecule in the oligomer is attached to one monosaccharide unit via an ether bond and the fourth ethanediol molecule in the oligomer is attached to an additional monosaccharide unit via an ether bond.

[0079] Referring again to FIG. 16, a portion 410 of the oligosaccharide produced by method 400 contains three different crosslinkable functional groups, as indicated by the labeled regions. These crosslinkable functional groups are attached to the monosaccharide units of the oligosaccharide via one linking group and to a single functionalized compound attached to the sugar of the monosaccharide via a further linking group, a single functionalized compound attached to two different monosaccharide units of the same oligosaccharide backbone, and two functionalized compounds linked together to form a crosslinkable functional group (in this case, the crosslinkable functional group is attached to one monosaccharide unit via one linking group and to a further monosaccharide unit via a second linking group). The functionalized compound used in method 400 is ethanediol, although it is understood that any of the functionalized compounds described herein or combinations thereof may be used. Although multiple crosslinkable functional groups are present in portion 410 of the oligosaccharide, it is further understood that the number and type of crosslinkable functional groups may be varied in other variations of method 400.

[0080] It is understood that any functionalized compound having two or more functional groups capable of forming a bond with a monosaccharide can form a crosslinkable functional group. For example, the crosslinkable functional group can be selected from polycarboxylic acids (such as succinic acid, itaconic acid, malic acid, maleic acid, and adipic acid), polyols (such as sorbitol, xylitol, arabinitol, glycerol, erythritol, mannitol, galactitol, fucitol, iditol, inositol, volemitol, and lactitol), and amino acids (such as glutamic acid). In some variations, the functionalized oligosaccharide composition comprises one or more crosslinking groups selected from the group consisting of glucosamine, galactosamine, lactic acid, acetic acid, citric acid, pyruvic acid, succinic acid, glutamic acid, aspartic acid, glucuronic acid, itaconic acid, malic acid, maleic acid, adipic acid, sorbitol, xylitol, arabinitol, glycerol, erythritol, mannitol, galactitol, fucitol, iditol, inositol, volemitol, lactitol, propanediol, butanediol, pentanediol, sulfate, and phosphate.

[0081] A functionalized oligosaccharide composition comprising a mixture of pendant functional groups and crosslinkable functional groups can also be produced using the methods described herein. For example, in certain embodiments, one or more sugars are combined with a polyol in the presence of a catalyst to produce a functionalized oligosaccharide composition, wherein at least a portion of the composition comprises pendant polyol functional groups attached to the oligosaccharide via an ether linkage group and at least a portion comprises crosslinkable polyol functional groups, wherein each group is attached to a first oligosaccharide via a first ether linkage group and to a second oligosaccharide via a second ether linkage group.

[0082] One or more functionalized compounds combined with a sugar, an oligosaccharide composition, or a combination thereof can form a bond with other functionalized compounds such that the functionalized oligosaccharide composition comprises monosaccharide units attached to the first functionalized compound, it being further understood that the first functionalized compound is attached to the second functionalized compound.

[0083] Catalyst The catalysts used in the methods described herein include polymeric catalysts and solid-supported catalysts.

[0084] In some embodiments, the catalyst is a polymer composed of acidic monomers and ionic monomers (which are also referred to herein as "ionomers") linked to form a polymer backbone. Each acidic monomer contains at least one Bronsted-Lowry acid, and each ionic monomer contains at least one nitrogen-containing cationic group, at least one phosphorus-containing cationic group, or any combination thereof. In certain embodiments of the polymer catalyst, at least some of the acidic monomers and ionic monomers can independently include a linker that links the Bronsted-Lowry acid or cationic group (where applicable) to a portion of the polymer backbone. In the case of acidic monomers, the Bronsted-Lowry acid and the linker together form a side chain. Similarly, in the case of ionic monomers, the cationic group and the linker together form a side chain. Referring to a portion of the polymer catalyst illustrated in FIGS. 2A and 2B, the side chains are pendant from the polymer backbone.

[0085] In another aspect, the catalyst is supported on a solid and has acidic sites and ionic sites each bonded to the solid support. Each acidic site independently contains at least one Bronsted-Lowry acid, and each ionic site contains at least one nitrogen-containing cationic group, at least one phosphorus-containing cationic group, or any combination thereof. In certain embodiments of the solid-supported catalyst, at least some of the acidic sites and ionic sites can independently include a linker that links the Bronsted-Lowry acid or cationic group (where applicable) to the solid support. Referring to FIG. 3, the resulting catalyst is a solid-supported catalyst having acidic sites and ionic sites.

[0086] Acidic Monomers and Sites The polymer catalyst contains a plurality of acidic monomers, while the solid-supported catalyst contains a plurality of acidic sites bonded to the solid support.

[0087] In some embodiments, a plurality of acidic monomers (e.g., of a polymeric catalyst) or a plurality of acidic sites (e.g., of a solid-supported catalyst) have at least one Bronsted-Lowry acid. In certain embodiments, a plurality of acidic monomers (e.g., of a polymeric catalyst) or a plurality of acidic sites (e.g., of a solid-supported catalyst) have one Bronsted-Lowry acid or two Bronsted-Lowry acids. In certain embodiments, a plurality of acidic monomers (e.g., of a polymeric catalyst) or a plurality of acidic sites (e.g., of a solid-supported catalyst) have one Bronsted-Lowry acid, while another has two Bronsted-Lowry acids.

[0088] In some embodiments, each Bronsted-Lowry acid is independently selected from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, and boronic acid. In certain embodiments, each Bronsted-Lowry acid is independently a sulfonic acid or a phosphonic acid. In one embodiment, each Bronsted-Lowry acid is a sulfonic acid. It is understood that the Bronsted-Lowry acids in the acidic monomers (e.g., of a polymeric catalyst) or acidic sites (e.g., of a solid-supported catalyst) may be the same for each occurrence or may differ in one or more occurrences.

[0089] In some embodiments, one or more acidic monomers of the polymeric catalyst are directly linked to the polymer backbone or one or more acidic sites of the solid-supported catalyst are directly linked to the solid support. In other embodiments, one or more acidic monomers (e.g., of a polymeric catalyst) or one or more acidic sites (e.g., of a solid-supported catalyst) each independently further comprise a linker that links the Bronsted-Lowry acid to the polymer backbone or the solid support (as appropriate). In certain embodiments, some of the Bronsted-Lowry acids are directly linked to the polymer backbone or the solid support (as appropriate), while other Bronsted-Lowry acids are linked to the polymer backbone or the solid support (as appropriate) by a linker.

[0090] In embodiments where the Brønsted-Lowry acid is linked to the polymer backbone or a solid support (if any) by a linker, each linker is independently selected from an unsubstituted or substituted alkyl linker, an unsubstituted or substituted cycloalkyl linker, an unsubstituted or substituted alkenyl linker, an unsubstituted or substituted aryl linker, and an unsubstituted or substituted heteroaryl linker. In certain embodiments, the linker is an unsubstituted or substituted aryl linker, or an unsubstituted or substituted heteroaryl linker. In certain embodiments, the linker is an unsubstituted or substituted aryl linker. In one embodiment, the linker is a phenyl linker. In another embodiment, the linker is a hydroxyl-substituted phenyl linker.

[0091] In other embodiments, the linkers in the acidic monomers (e.g., of a polymeric catalyst) or acidic sites (e.g., of a solid-supported catalyst) are each an unsubstituted alkyl linker, an alkyl linker substituted with 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino, an unsubstituted cycloalkyl linker, a cycloalkyl linker substituted with 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino, an unsubstituted alkenyl linker, an alkenyl linker substituted with 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino, an unsubstituted aryl linker, an aryl linker substituted with 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino, an unsubstituted heteroaryl linker, or a heteroaryl linker substituted with 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino and are independently selected from.

[0092] Furthermore, it is understood that some or all of the acidic monomers (e.g., of a polymeric catalyst) or one or more acidic sites (e.g., of a solid-supported catalyst) linked to the polymer backbone by a linker may have the same linker or may independently have different linkers.

[0093] In some embodiments, each acidic monomer (e.g., of a polymeric catalyst) and each acidic site (e.g., of a solid-supported catalyst) has a structure of Formulas IA-VIA:

[0094]

Chemical formula

[0095] In some embodiments, each acidic monomer (e.g., of a polymeric catalyst) and each acidic site (e.g., of a solid-supported catalyst) can independently have a structure of Formula IA, IB, IVA, or IVB. In other embodiments, each acidic monomer (e.g., of a polymeric catalyst) and each acidic site (e.g., of a solid-supported catalyst) can independently have a structure of Formula IIA, IIB, IIC, IVA, IVB, or IVC. In other embodiments, each acidic monomer (e.g., of a polymeric catalyst) and each acidic site (e.g., of a solid-supported catalyst) can independently have a structure of Formula IIIA, IIIB, or IIIC. In some embodiments, each acidic monomer (e.g., of a polymeric catalyst) and each acidic site (e.g., of a solid-supported catalyst) can independently have a structure of Formula VA, VB, or VC. In some embodiments, each acidic monomer (e.g., of a polymeric catalyst) and each acidic site (e.g., of a solid-supported catalyst) can independently have a structure of Formula IA. In other embodiments, each acidic monomer (e.g., of a polymeric catalyst) and each acidic site (e.g., of a solid-supported catalyst) can independently have a structure of Formula IB.

[0096] In some embodiments, Z can be selected from C(R 2 )(R 3 ), N(R 4 ), SO 2 and O. In some embodiments, any two adjacent Z's can together form a group selected from heterocycloalkyl, aryl, and heteroaryl. In other embodiments, any two adjacent Z's can be joined by a double bond. Any combination of these embodiments is also contemplated (as chemically feasible).

[0097] In some embodiments, m is 2 or 3. In other embodiments, n is 1, 2, or 3. In some embodiments, R 1 can be hydrogen, alkyl, or heteroalkyl. In some embodiments, R 1can be hydrogen, methyl or ethyl. In some embodiments, R 2 , R 3 and R 4 can each independently be hydrogen, alkyl, heterocyclyl, aryl or heteroaryl. In other embodiments, R 2 , R 3 and R 4 can each independently be heteroalkyl, cycloalkyl, heterocyclyl or heteroaryl. In some embodiments, R 5 and R 6 can each independently be alkyl, heterocyclyl, aryl or heteroaryl. In another embodiment, any two adjacent Zs can together form cycloalkyl, heterocycloalkyl, aryl or heteroaryl.

[0098] In some embodiments, the polymeric catalysts and solid supported catalysts described herein each contain a monomer or moiety having at least one Bronsted-Lowry acid and at least one cationic group. The Bronsted-Lowry acid and the cationic group can be on different monomers / moieties or on the same monomer / moiety.

[0099] In certain embodiments, the acidic monomer of the polymeric catalyst can have a side chain having a Bronsted-Lowry acid linked to the polymer backbone by a linker. In certain embodiments, the acidic site of the solid supported catalyst can have a Bronsted-Lowry acid bonded to the solid support by a linker. The side chain (e.g., of the polymeric catalyst) or the acidic site (e.g., of the solid supported catalyst) having one or more Bronsted-Lowry acids linked by a linker can be, for example,

[0100]

Chemical formula

[0101] In certain embodiments, L is an alkyl linker. In other embodiments, L is methyl, ethyl, propyl, butyl. In still other embodiments, the linker is ethanoyl, propanoyl, benzoyl. In certain embodiments, r is 1, 2, 3, 4 or 5 (when applicable or chemically achievable).

[0102] In some embodiments, at least a portion of the acidic side chains (e.g., of a polymeric catalyst) and at least a portion of the acidic sites (e.g., of a solid supported catalyst) are

[0103]

Chemical formula

[0104] In certain embodiments, s is from 1 to 9, or from 1 to 8, or from 1 to 7, or from 1 to 6, or from 1 to 5, or from 1 to 4, or from 1 to 3, or 2, or 1. In certain embodiments, w is from 0 to 9, or from 0 to 8, or from 0 to 7, or from 0 to 6, or from 0 to 5, or from 0 to 4, or from 0 to 3, or from 0 to 2, 1, or 0.

[0105] In certain embodiments, at least a portion of the acidic side chains (e.g., of a polymeric catalyst) and at least a portion of the acidic sites (e.g., of a solid supported catalyst) are

[0106]

Chemical formula

[0107] In other embodiments, the acidic monomer (e.g., of a polymeric catalyst) can have a side chain having a Bronsted-Lowry acid directly linked to the polymer backbone. In other embodiments, the acidic site (e.g., of a solid-supported catalyst) can be directly linked to the solid support. The side chain directly linked to the polymer backbone (e.g., of a polymeric catalyst), or the acidic site (e.g., of a solid-supported catalyst) directly bonded to the solid support can, for example,

[0108] [Chemical formula] can include.

[0109] Ionic monomers and sites The polymeric catalyst includes a plurality of ionic monomers, while the solid-supported catalyst includes a plurality of ionic sites bonded to the solid support.

[0110] In some embodiments, the plurality of ionic monomers (e.g., of a polymeric catalyst) or the plurality of ionic sites (e.g., of a solid-supported catalyst) have at least one nitrogen-containing cationic group, at least one phosphorus-containing cationic group, or any combination thereof. In certain embodiments, the plurality of ionic monomers (e.g., of a polymeric catalyst) or the plurality of ionic sites (e.g., of a solid-supported catalyst) have one nitrogen-containing cationic group or one phosphorus-containing cationic group. In some embodiments, the plurality of ionic monomers (e.g., of a polymeric catalyst) or the plurality of ionic sites (e.g., of a solid-supported catalyst) have two nitrogen-containing cationic groups, two phosphorus-containing cationic groups, or one nitrogen-containing cationic group and one phosphorus-containing cationic group. In other embodiments, the plurality of ionic monomers (e.g., of a polymeric catalyst) or the plurality of ionic sites (e.g., of a solid-supported catalyst) have one nitrogen-containing cationic group or phosphorus-containing cationic group, while another has two nitrogen-containing cationic groups or phosphorus-containing cationic groups.

[0111] In some embodiments, the plurality of ionic monomers (e.g., of a polymeric catalyst) or the plurality of ionic sites (e.g., of a solid-supported catalyst) can have one cationic group, or two or more cationic groups (if chemically feasible). When the ionic monomer (e.g., of a polymeric catalyst) or the ionic site (e.g., of a solid-supported catalyst) has two or more cationic groups, these cationic groups can be the same or different.

[0112] In some embodiments, each ionic monomer (e.g., of a polymeric catalyst) or each ionic site (e.g., of a solid-supported catalyst) is a nitrogen-containing cationic group. In other embodiments, each ionic monomer (e.g., of a polymeric catalyst) or each ionic site (e.g., of a solid-supported catalyst) is a phosphorus-containing cationic group. In still other embodiments, at least a portion of the ionic monomers (e.g., of a polymeric catalyst) or at least a portion of the ionic sites (e.g., of a solid-supported catalyst) are nitrogen-containing cationic groups, while the cationic groups in other ionic monomers (e.g., of a polymeric catalyst) or ionic sites (e.g., of a solid-supported catalyst) are phosphorus-containing cationic groups. In an exemplary embodiment, the cationic groups in the polymeric catalyst or the solid-supported catalyst are each imidazolium. In another exemplary embodiment, the cationic groups in some monomers (e.g., of a polymeric catalyst) or sites (e.g., of a solid-supported catalyst) are imidazolium, while the cationic groups in other monomers (e.g., of a polymeric catalyst) or sites (e.g., of a solid-supported catalyst) are pyridinium. In yet another exemplary embodiment, the cationic groups in the polymeric catalyst or the solid-supported catalyst are each substituted phosphonium. In yet another exemplary embodiment, the cationic groups in some monomers (e.g., of a polymeric catalyst) or sites (e.g., of a solid-supported catalyst) are triphenylphosphonium, while the cationic groups in other monomers (e.g., of a polymeric catalyst) or sites (e.g., of a solid-supported catalyst) are imidazolium.

[0113] In some embodiments, the nitrogen-containing cationic group can be independently selected, each occurrence, from pyrrolidium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyrazidimium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrrolidinium. In other embodiments, the nitrogen-containing cationic group can be independently selected, each occurrence, from imidazolium, pyridinium, pyrimidinium, morpholinium, piperidinium, and piperidinium. In some embodiments, the nitrogen-containing cationic group can be imidazolium.

[0114] In some embodiments, the phosphorus-containing cationic group can be independently selected, each occurrence, from triphenylphosphonium, trimethylphosphonium, triethylphosphonium, tripropylphosphonium, tributylphosphonium, trichlorophosphonium, and trifluorophosphonium. In other embodiments, the phosphorus-containing cationic group can be independently selected, each occurrence, from triphenylphosphonium, trimethylphosphonium, and triethylphosphonium. In other embodiments, the phosphorus-containing cationic group can be triphenylphosphonium.

[0115] In some embodiments, one or more ionic monomers of the polymer catalyst are directly linked to the polymer backbone, or one or more ionic sites of the supported solid catalyst are directly linked to the solid support. In other embodiments, one or more ionic monomers (e.g., of the polymer catalyst) or one or more ionic sites (e.g., of the supported solid catalyst) each independently further comprise a linker that attaches the cationic group to the polymer backbone or solid support (as appropriate). In certain embodiments, some of the cationic groups are directly linked to the polymer backbone or solid support (as appropriate), while other cationic groups are linked to the polymer backbone or solid support (as appropriate) by a linker.

[0116] In embodiments where the cationic group is linked to the polymer backbone or a solid support (as appropriate) by a linker, each linker is independently selected from an unsubstituted or substituted alkyl linker, an unsubstituted or substituted cycloalkyl linker, an unsubstituted or substituted alkenyl linker, an unsubstituted or substituted aryl linker, and an unsubstituted or substituted heteroaryl linker. In certain embodiments, the linker is an unsubstituted or substituted aryl linker, or an unsubstituted or substituted heteroaryl linker. In certain embodiments, the linker is an unsubstituted or substituted aryl linker. In one embodiment, the linker is a phenyl linker. In another embodiment, the linker is a hydroxyl-substituted phenyl linker.

[0117] In other embodiments, the linkers in the ionic monomer (e.g., of a polymer catalyst) or the ionic sites (e.g., of a solid-supported catalyst) are each an unsubstituted alkyl linker, an alkyl linker substituted with 1 to 5 substituents independently selected from oxo, hydroxy, halo, and amino, an unsubstituted cycloalkyl linker, a cycloalkyl linker substituted with 1 to 5 substituents independently selected from oxo, hydroxy, halo, and amino, an unsubstituted alkenyl linker, an alkenyl linker substituted with 1 to 5 substituents independently selected from oxo, hydroxy, halo, and amino, an unsubstituted aryl linker, an aryl linker substituted with 1 to 5 substituents independently selected from oxo, hydroxy, halo, and amino, an unsubstituted heteroaryl linker, or a heteroaryl linker substituted with 1 to 5 substituents independently selected from oxo, hydroxy, halo, and amino and are independently selected from.

[0118] Furthermore, some or all of the ionic monomers (e.g., of a polymer catalyst) or one or more ionic sites (e.g., of a solid-supported catalyst) linked to the polymer backbone by a linker may have the same linker or may independently have different linkers.

[0119] In some embodiments, each ionic monomer (e.g., of a polymer catalyst) or each ionic site (e.g., of a solid-supported catalyst) has a structure of Formulas VIIA - XIB:

[0120]

Chemical Formula

[0121] In some embodiments, Z can be selected from C(R 2 )(R 3 ), N(R 4 ), SO 2 , and O. In some embodiments, any two adjacent Zs can together form a group selected from heterocycloalkyl, aryl and heteroaryl. In other embodiments, any two adjacent Zs can be bonded by a double bond. In some embodiments, each X can be Cl - , NO 3 - , SO 4 2- , R 7 SO 4 - or R 7 CO 2 - , where R 7 is hydrogen or C 1~4It can be alkyl. In another embodiment, each of X is Cl - 、Br - 、 I - 、HSO 4 - 、HCO 2 - 、CH 3 CO 2 - or NO 3 - and can be. In other embodiments, X is an acetate ion. In other embodiments, X is a bisulfate ion. In other embodiments, X is a chloride ion. In other embodiments, X is a nitrate ion.

[0122] In some embodiments, m is 2 or 3. In other embodiments, n is 1, 2, or 3. In some embodiments, R 2 、R 3 and R 4 can each independently be hydrogen, alkyl, heterocyclyl, aryl, or heteroaryl. In other embodiments, R 2 、R 3 and R 4 can each independently be heteroalkyl, cycloalkyl, heterocyclyl, or heteroaryl. In some embodiments, R 5 and R 6 can each independently be alkyl, heterocyclyl, aryl, or heteroaryl. In another embodiment, any two adjacent Zs can together form cycloalkyl, heterocycloalkyl, aryl or heteroaryl.

[0123] In certain embodiments, the ionic monomer of the polymeric catalyst can have a side chain having a cationic group linked to the polymer backbone by a linker. In certain embodiments, the ionic site of the solid-supported catalyst can have a cationic group bonded to the solid support by a linker. A side chain (e.g., of a polymeric catalyst) or an ionic site (e.g., of a solid-supported catalyst) having one or more cationic groups linked by a linker can be, for example,

[0124] [Chemical Formula] (wherein L is an unsubstituted alkyl linker, an alkyl linker substituted by oxo, an unsubstituted cycloalkyl, an unsubstituted aryl, an unsubstituted heterocycloalkyl, and an unsubstituted heteroaryl, R 1a , R 1b and R 1c are each independently hydrogen or alkyl, or R 1a and R 1b together with the nitrogen atom to which they are attached form an unsubstituted heterocycloalkyl, or R 1a and R 1b together with the nitrogen atom to which they are attached form an unsubstituted heteroaryl or a substituted heteroaryl, and R 1c is absent, r is an integer, X is as described above for Formulas VIIA-XIB) and can include.

[0125] In other embodiments, L is methyl, ethyl, propyl, butyl. In still other embodiments, the linker is ethanoyl, propanoyl, benzoyl. In certain embodiments, r is 1, 2, 3, 4 or 5 (when applicable or chemically feasible).

[0126] In other embodiments, the linkers are each an unsubstituted alkyl linker, An alkyl linker substituted with 1 to 5 substituents independently selected from oxo, hydroxy, halo, and amino, An unsubstituted cycloalkyl linker, A cycloalkyl linker substituted with 1 to 5 substituents independently selected from oxo, hydroxy, halo, and amino, An unsubstituted alkenyl linker, An alkenyl linker substituted with 1 to 5 substituents independently selected from oxo, hydroxy, halo, and amino, An unsubstituted aryl linker, An aryl linker substituted with 1 to 5 substituents independently selected from oxo, hydroxy, halo, and amino, An unsubstituted heteroaryl linker, or A heteroaryl linker substituted with 1 to 5 substituents independently selected from oxo, hydroxy, halo, and amino is independently selected from.

[0127] In certain embodiments, each linker is an unsubstituted alkyl linker or an alkyl linker having an oxo substituent. In one embodiment, each linker is —(CH 2 )(CH 2 )— or —(CH 2 )(C═O). In certain embodiments, r is 1, 2, 3, 4, or 5 (when applicable or chemically feasible).

[0128] In some embodiments, at least a portion of the ionic side chains (e.g., of a polymeric catalyst) and at least a portion of the ionic sites (e.g., of a solid-supported catalyst) are

[0129]

Chemical formula

[0130] In certain embodiments, s is from 1 to 9, or from 1 to 8, or from 1 to 7, or from 1 to 6, or from 1 to 5, or from 1 to 4, or from 1 to 3, or 2, or 1. In certain embodiments, v is from 0 to 9, or from 0 to 8, or from 0 to 7, or from 0 to 6, or from 0 to 5, or from 0 to 4, or from 0 to 3, or from 0 to 2, 1, or 0.

[0131] In certain embodiments, at least a portion of the ionic side chains (e.g., of a polymeric catalyst) and at least a portion of the ionic sites (e.g., of a solid supported catalyst) are

[0132]

Chemical formula

[0133] In other embodiments, the ionic monomer (e.g., of a polymeric catalyst) can have a side chain having a cationic group directly linked to the polymer backbone. In other embodiments, the ionic site (e.g., of a solid-supported catalyst) can have a cationic group directly bonded to the solid support. The side chain directly linked to the polymer backbone (e.g., of a polymeric catalyst), or the ionic site directly bonded to the solid support (e.g., of a solid-supported catalyst) can, for example,

[0134] [Chemical formula] can include.

[0135] In some embodiments, the nitrogen-containing cationic group can be an N-oxide, in which case the negatively charged oxide (O-) cannot readily dissociate from the nitrogen cation. Non-limiting examples of such groups include, for example,

[0136] [Chemical formula] are included.

[0137] In some embodiments, the phosphorus-containing side chain (e.g., of a polymeric catalyst) or the site (e.g., of a solid-supported catalyst) is independently

[0138] [Chemical formula] is.

[0139] In other embodiments, the ionic monomer (e.g., of a polymeric catalyst) can have a side chain having a cationic group directly linked to the polymer backbone. In other embodiments, the ionic site (e.g., of a solid-supported catalyst) can have a cationic group directly bonded to the solid support. The side chain directly linked to the polymer backbone (e.g., of a polymeric catalyst), or the ionic site directly bonded to the solid support (e.g., of a solid-supported catalyst) can, for example,

[0140]

Chem.

[0141] (For example, of a polymer catalyst) the ionic monomers or (for example, of a solid-supported catalyst) the ionic sites can all have the same cationic group or can have different cationic groups. In some embodiments, the cationic groups in the polymer catalyst or solid-supported catalyst are each nitrogen-containing cationic groups. In other embodiments, the cationic groups in the polymer catalyst or solid-supported catalyst are each phosphorus-containing cationic groups. In still other embodiments, the cationic groups in some monomers or sites of the polymer catalyst or solid-supported catalyst are each nitrogen-containing cationic groups, while the cationic groups in other monomers or sites of the polymer catalyst or solid-supported catalyst are each phosphorus-containing cationic groups. In an exemplary embodiment, the cationic groups in the polymer catalyst or solid-supported catalyst are each imidazolium. In another exemplary embodiment, the cationic groups in some monomers or sites of the polymer catalyst or solid-supported catalyst are imidazolium, while the cationic groups in other monomers or sites of the polymer catalyst or solid-supported catalyst are pyridinium. In yet another exemplary embodiment, the cationic groups in the polymer catalyst or solid-supported catalyst are each substituted phosphonium. In yet another exemplary embodiment, the cationic groups in some monomers or sites of the polymer catalyst or solid-supported catalyst are triphenylphosphonium, while the cationic groups in other monomers or sites of the polymer catalyst or solid-supported catalyst are imidazolium.

[0142] Acidic-ionic monomers and sites Some of the monomers in the polymeric catalyst contain both a Bronsted-Lowry acid and a cationic group within the same monomer. Such monomers are referred to as "acidic-ionic monomers". Similarly, some of the sites in the solid-supported catalyst contain both a Bronsted-Lowry acid and a cationic group within the same site. Such sites are referred to as "acidic-ionic sites". For example, in an exemplary embodiment, the acidic-ionic monomer (e.g., of a polymeric catalyst) or the acidic-ionic site (e.g., of a solid-supported catalyst) can contain imidazolium and acetic acid, or pyridinium and boronic acid.

[0143] In some embodiments, the monomer (e.g., of a polymeric catalyst) or the site (e.g., of a solid-supported catalyst) contains both one or more Bronsted-Lowry acids and one or more cationic groups, where the Bronsted-Lowry acid is linked by a linker to either the polymer backbone (e.g., of a polymeric catalyst) or the solid support (e.g., of a solid-supported catalyst), and / or the cationic group is linked by a linker to the polymer backbone (e.g., of a polymeric catalyst) or is attached to the solid support (e.g., of a solid-supported catalyst).

[0144] It is understood that any of the Bronsted-Lowry acids, cationic groups, and linkers (when present) suitable for acidic monomers / sites and / or ionic monomers / sites can be used for acidic-ionic monomers / sites.

[0145] In certain embodiments, the Bronsted-Lowry acid in the acidic-ionic monomer (e.g., of a polymeric catalyst) or acidic-ionic site (e.g., of a solid-supported catalyst) is independently selected, each occurrence, from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, and boric acid. In certain embodiments, the Bronsted-Lowry acid in the acidic-ionic monomer (e.g., of a polymeric catalyst) or acidic-ionic site (e.g., of a solid-supported catalyst) is, each occurrence, independently a sulfonic acid or a phosphonic acid. In one embodiment, the Bronsted-Lowry acid in the acidic-ionic monomer (e.g., of a polymeric catalyst) or acidic-ionic site (e.g., of a solid-supported catalyst) is, each occurrence, a sulfonic acid.

[0146] In some embodiments, the nitrogen-containing cationic group in the acidic-ionic monomer (e.g., of a polymeric catalyst) or acidic-ionic site (e.g., of a solid-supported catalyst) is independently selected, each occurrence, from pyrrolidium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyrazidimium, thiazinium, morpholinium, piperidinium, piperidinium, and pyrrolidinium. In one embodiment, the nitrogen-containing cationic group is imidazolium.

[0147] In some embodiments, the phosphorus-containing cationic group in the acidic-ionic monomer (e.g., of a polymeric catalyst) or acidic-ionic site (e.g., of a solid-supported catalyst) is independently selected, each occurrence, from triphenylphosphonium, trimethylphosphonium, triethylphosphonium, tripropylphosphonium, tributylphosphonium, trichlorophosphonium, and trifluorophosphonium. In one embodiment, the phosphorus-containing cationic group is triphenylphosphonium.

[0148] In some embodiments, the polymeric catalyst or the solid-supported catalyst can each include at least one acidic-ionic monomer or site linked to the polymer backbone or the solid support, where the at least one acidic-ionic monomer or site includes at least one Bronsted-Lowry acid and at least one cationic group, and at least one of the acidic-ionic monomers or sites includes a linker that links the acidic-ionic monomer to the polymer backbone or the solid support. The cationic group can be a nitrogen-containing cationic group or a phosphorus-containing cationic group as described herein. The linker can also be as described herein for either the acidic site or the ionic site. For example, the linker can be selected from unsubstituted or substituted alkyl linkers, unsubstituted or substituted cycloalkyl linkers, unsubstituted or substituted alkenyl linkers, unsubstituted or substituted aryl linkers, and unsubstituted or substituted heteroaryl linkers.

[0149] In other embodiments, the monomer (e.g., of the polymeric catalyst) or the site (e.g., of the solid-supported catalyst) can have a side chain containing both a Bronsted-Lowry acid and a cationic group, where the Bronsted-Lowry acid is directly linked to the polymer backbone or the solid support, the cationic group is directly linked to the polymer backbone or the solid support, or both the Bronsted-Lowry acid and the cationic group are directly linked to the polymer backbone or the solid support.

[0150] In certain embodiments, the linker is an unsubstituted or substituted aryl linker or an unsubstituted or substituted heteroaryl linker. In certain embodiments, the linker is an unsubstituted or substituted aryl linker. In one embodiment, the linker is a phenyl linker. In another embodiment, the linker is a hydroxyl-substituted phenyl linker.

[0151] Monomers of a polymer catalyst having a side chain containing both a Bronsted-Lowry acid and a cationic group can also be referred to as "acidic ionomers". The acidic-ionic side chains (e.g., of a polymer catalyst) or acidic-ionic sites (e.g., of a solid-supported catalyst) linked by a linker are, for example,

[0152]

Chemical formula

[0153] In some embodiments, R 1can be selected from hydrogen, alkyl, and heteroalkyl. In some embodiments, R 1 can be selected from hydrogen, methyl, or ethyl. In some embodiments, each X is Cl - , NO 3 - , SO 4 2- , R 7 SO 4 - , and R 7 CO 2 - , where R 7 can be selected from hydrogen and C 1~4 alkyl. In another embodiment, each X is Cl - , Br - 、 I - , HSO 4 - , HCO 2 - , CH 3 CO 2 - , and NO 3 - . In other embodiments, X is an acetate ion. In other embodiments, X is a bisulfate ion. In other embodiments, X is a chloride ion. In other embodiments, X is a nitrate ion.

[0154] In some embodiments, the acidic-ionic side chains (e.g., of a polymeric catalyst) or the acidic-ionic sites (e.g., of a solid-supported catalyst) are independently

[0155]

Chemical formula

[0156] In some embodiments, the acidic-ionic side chains (e.g., of a polymeric catalyst) or the acidic-ionic sites (e.g., of a solid-supported catalyst) are independently

[0157]

Chemical formula

[0158] In other embodiments, the monomers (e.g., of a polymeric catalyst) or sites (e.g., of a solid-supported catalyst) can have both a Bronsted-Lowry acid and a cationic group, in which case the Bronsted-Lowry acid is directly linked to the polymer backbone or the solid support, the cationic group is directly linked to the polymer backbone or the solid support, or both the Bronsted-Lowry acid and the cationic group are directly linked to the polymer backbone or the solid support. Such side chains in the acidic-ionic monomers (e.g., of a polymeric catalyst) or sites (e.g., of a solid-supported catalyst) can include, for example,

[0159]

Chemical formula

[0160] Hydrophobic monomers and sites In some embodiments, the polymeric catalyst further includes hydrophobic monomers linked to form a polymer backbone. Similarly, in some embodiments, the solid-supported catalyst further includes hydrophobic sites bonded to the solid support. In either case, each hydrophobic monomer or site has at least one hydrophobic group. In certain embodiments of the polymeric catalyst or the solid-supported catalyst, each hydrophobic monomer or site has one hydrophobic group. In certain embodiments of the polymeric catalyst or the solid-supported catalyst, the hydrophobic monomers or sites each have two hydrophobic groups. In other embodiments of the polymeric catalyst or the solid-supported catalyst, some of the hydrophobic monomers or sites have one hydrophobic group while others have two hydrophobic groups.

[0161] In some embodiments of the polymeric catalyst or the solid-supported catalyst, each hydrophobic group is independently selected from unsubstituted or substituted alkyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, and unsubstituted or substituted heteroaryl. In certain embodiments of the polymeric catalyst or the solid-supported catalyst, each hydrophobic group is unsubstituted or substituted aryl, or unsubstituted or substituted heteroaryl. In one embodiment, each hydrophobic group is phenyl. Further, it is understood that the hydrophobic monomers may all have the same hydrophobic group or may have different hydrophobic groups.

[0162] In some embodiments of the polymeric catalyst, the hydrophobic groups are linked directly to form the polymer backbone. In some embodiments of the solid-supported catalyst, the hydrophobic groups are directly bonded to the solid support.

[0163] Other features of the catalyst In some embodiments, the acidic monomers and the ionic monomers constitute a substantial portion of the polymeric catalyst. In some embodiments, the acidic sites and the ionic sites constitute a substantial portion of the solid-supported catalyst. In certain embodiments, the acidic and ionic monomers or sites constitute at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 99% of the monomers or sites of the catalyst, based on the ratio of the number of acidic and ionic monomers / sites to the total number of monomers / sites present in the catalyst.

[0164] In some embodiments, the polymeric catalyst or the solid-supported catalyst has a total amount of Bronsted-Lowry acid of about 0.1 to about 20 mmol, about 0.1 to about 15 mmol, about 0.01 to about 12 mmol, about 0.05 to about 10 mmol, about 1 to about 8 mmol, about 2 to about 7 mmol, about 3 to about 6 mmol, about 1 to about 5, or about 3 to about 5 mmol per gram of the polymeric catalyst or the solid-supported catalyst.

[0165] In some embodiments of the polymeric catalyst or the solid-supported catalyst, each ionic monomer further comprises a counterion for each nitrogen-containing cationic group or phosphorus-containing cationic group. In certain embodiments of the polymeric catalyst or the solid-supported catalyst, each counterion is independently selected from halide ions, nitrate ions, sulfate ions, formate ions, acetate ions, or organic sulfonate ions. In some embodiments of the polymeric catalyst or the solid-supported catalyst, the counterion is a fluoride ion, a chloride ion, a bromide ion, or an iodide ion. In one embodiment of the polymeric catalyst or the solid-supported catalyst, the counterion is a chloride ion. In another embodiment of the polymeric catalyst or the solid-supported catalyst, the counterion is a sulfate ion. In yet another embodiment of the polymeric catalyst or the solid-supported catalyst, the counterion is an acetate ion.

[0166] In some embodiments, the polymeric catalyst or the solid-supported catalyst has a total amount of nitrogen-containing cationic groups and counterions, or a total amount of phosphorus-containing cationic groups and counterions, of about 0.01 to about 10 mmol, about 0.05 to about 10 mmol, about 1 to about 8 mmol, about 2 to about 6 mmol, or about 3 to about 5 mmol per gram of the polymeric catalyst or the solid-supported catalyst.

[0167] In some embodiments, the acidic monomer and the ionic monomer constitute a substantial portion of the polymeric catalyst or the solid-supported catalyst. In certain embodiments, the acidic and ionic monomers or sites constitute at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 99% of the monomers or sites in the polymeric catalyst or the solid-supported catalyst, based on the ratio of the number of acidic and ionic monomers or sites to the total number of monomers or sites present in the polymeric catalyst or the solid-supported catalyst.

[0168] The ratio of the total number of acidic monomers or acidic sites to the total number of ionic monomers or ionic sites can be varied to adjust the catalyst strength. In some embodiments, the total number of acidic monomers or acidic sites exceeds the total number of ionic monomers or ionic sites in the polymer or solid support. In other embodiments, the total number of acidic monomers or acidic sites is at least about 2 times, at least about 3 times, at least about 4 times, at least about 5 times, at least about 6 times, at least about 7 times, at least about 8 times, at least about 9 times, or at least about 10 times the total number of ionic monomers or ionic sites in the polymer catalyst or solid-supported catalyst. In certain embodiments, the ratio of the total number of acidic monomers or acidic sites to the total number of ionic monomers or ionic sites is about 1:1, about 2:1, about 3:1, about 4:1, about 5:1, about 6:1, about 7:1, about 8:1, about 9:1, or about 10:1.

[0169] In some embodiments, the total number of ionic monomers or ionic sites exceeds the total number of acidic monomers or acidic sites in the catalyst. In other embodiments, the total number of ionic monomers or ionic sites is at least about 2 times, at least about 3 times, at least about 4 times, at least about 5 times, at least about 6 times, at least about 7 times, at least about 8 times, at least about 9 times, or at least about 10 times the total number of acidic monomers or acidic sites in the polymer catalyst or solid-supported catalyst. In certain embodiments, the ratio of the total number of ionic monomers or ionic sites to the total number of acidic monomers or acidic sites is about 1:1, about 2:1, about 3:1, about 4:1, about 5:1, about 6:1, about 7:1, about 8:1, about 9:1, or about 10:1.

[0170] Arrangement of monomers in the polymer catalyst In some embodiments of the polymer catalyst, the acidic monomers, ionic monomers, acidic-ionic monomers, and hydrophobic monomers (if present) can be arranged as blocks of monomers, in an alternating arrangement or in a random order. In some embodiments, each block has 20 or fewer, 15 or fewer, 10 or fewer, 6 or fewer, or 3 or fewer monomers.

[0171] In some embodiments of the polymer catalyst, the monomers of the polymer catalyst are randomly arranged in an alternating sequence. Referring to a portion of the polymer catalyst illustrated in FIG. 9, the monomers are randomly arranged in an alternating sequence.

[0172] In other embodiments of the polymer catalyst, the monomers of the polymer catalyst are randomly arranged as blocks of monomers. Referring to a portion of the polymer catalyst illustrated in FIG. 4, the monomers are arranged within blocks of monomers. In certain embodiments where acidic monomers and ionic monomers are arranged within blocks of monomers, each block has 20 or fewer, 19 or fewer, 18 or fewer, 17 or fewer, 16 or fewer, 15 or fewer, 14 or fewer, 13 or fewer, 12 or fewer, 11 or fewer, 10 or fewer, 9 or fewer, 8 or fewer, 7 or fewer, 6 or fewer, 5 or fewer, 4 or fewer, or 3 or fewer monomers.

[0173] The polymer catalysts described herein can also be crosslinked. Such crosslinked polymer catalysts can be prepared by introduction of crosslinking groups. In some embodiments, referring to a portion of the polymer catalyst illustrated in FIGS. 5A and 5B, crosslinking can be carried out within a given polymer chain. In other embodiments, referring to a portion of the polymer catalysts of FIGS. 6A, 6B, 6C, and 6D, crosslinking can be carried out between two or more polymer chains.

[0174] Referring to FIGS. 5A, 5B, and 6A, R 1 , R 2 and R 3It is to be understood that each is an exemplary crosslinking group. Suitable crosslinking groups that can be used to form a crosslinked polymer catalyst having the polymers described herein include, for example, substituted or unsubstituted divinylalkanes, substituted or unsubstituted divinylcycloalkanes, substituted or unsubstituted divinylaryls, substituted or unsubstituted heteroaryls, dihaloalkanes, dihaloalkenes, and dihaloalkynes, where these substituents are as defined herein. For example, crosslinking groups can include divinylbenzene, diallylbenzene, dichlorobenzene, divinylmethane, dichloromethane, divinylethane, dichloroethane, divinylpropane, dichloropropane, divinylbutane, dichlorobutane, ethylene glycol, and resorcinol. In one embodiment, the crosslinking group is divinylbenzene.

[0175] In some embodiments of the polymer catalyst, the polymer is crosslinked. In certain embodiments, at least about 1%, at least about 2%, at least about 3%, at least about 4%, at least about 5%, at least about 6%, at least about 7%, at least about 8%, at least about 9%, at least about 10%, at least about 15%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90% or at least about 99% of the polymer is crosslinked.

[0176] In some embodiments of the polymer catalyst, the polymers described herein are not substantially crosslinked, for example less than about 0.9% is crosslinked, less than about 0.5% is crosslinked, less than about 0.1% is crosslinked, less than about 0.01% is crosslinked, or less than 0.001% is crosslinked.

[0177] Polymer backbone In some embodiments, the polymer backbone is formed from one or more substituted or unsubstituted monomers. Polymerization methods using a wide range of monomers are well known in the art (see, e.g., International Union of Pure and Applied Chemistry, et al., IUPAC Gold Book, Polymerization. (2000)). One such method involves monomers having an unsaturated substituent, such as vinyl, propenyl, butenyl, or other such substituent(s). These types of monomers are capable of undergoing radical initiation and chain polymerization.

[0178] In some embodiments, the polymer backbone is formed from one or more substituted or unsubstituted monomers selected from ethylene, propylene, hydroxyethylene, acetaldehyde, styrene, divinylbenzene, isocyanate, vinyl chloride, vinylphenol, tetrafluoroethylene, butylene, terephthalic acid, caprolactam, acrylonitrile, butadiene, ammonia, diammonia, pyrrole, imidazole, pyrazole, oxazole, thiazole, pyridine, pyrimidine, pyrazine, pyrazidimine, thiazine, morpholine, piperidine, piperizine, pyrollizine, triphenylphosphonate, trimethylphosphonate, triethylphosphonate, tripropylphosphonate, tributylphosphonate, trichlorophosphonate, trifluorophosphonate, and diazole.

[0179] The polymer backbone of the polymer catalyst described in this specification can include, for example, polyalkylene, polyalkenyl alcohol, polycarbonate, polyarylene, polyaryl ether ketone, and polyamide-imide. In certain embodiments, the polymer backbone can be selected from polyethylene, polypropylene, polyvinyl alcohol, polystyrene, polyurethane, polyvinyl chloride, polyphenol-aldehyde, polytetrafluoroethylene, polybutylene terephthalate, polycaprolactam, and poly(acrylonitrile butadiene styrene). In certain embodiments of the polymer catalyst, the polymer backbone is polyethylene or polypropylene. In one embodiment of the polymer catalyst, the polymer backbone is polyethylene. In another embodiment of the polymer catalyst, the polymer backbone is polyvinyl alcohol. In yet another embodiment of the polymer catalyst, the polymer backbone is polystyrene.

[0180] Referring to FIG. 7, in one embodiment, the polymer backbone is polyethylene. Referring to FIG. 8, in another embodiment, the polymer backbone is polyvinyl alcohol.

[0181] The polymer backbone described in this specification can also include ionic groups integrated as part of the polymer backbone. Such polymer backbones can also be referred to as "ionomer backbones". In certain embodiments, the polymer backbone is Polyalkylene ammonium, polyalkylene diammonium, polyalkylene pyrrolinium, polyalkylene imidazolium, polyalkylene pyrazolinium, polyalkylene oxazolinium, polyalkylene thiazolinium, polyalkylene pyridinium, polyalkylene pyrimidinium, polyalkylene pyrazinium, polyalkylene pyrazidimium, polyalkylene thiazinium, polyalkylene morpholinium, polyalkylene piperidinium, polyalkylene piperidinium, polyalkylene pyrrolidinium, polyalkylene triphenylphosphonium, polyalkylene trimethylphosphonium, polyalkylene triethylphosphonium, polyalkylene tripropylphosphonium, polyalkylene tributylphosphonium, polyalkylene trichlorophosphonium, polyalkylene trifluorophosphonium, and polyalkylene diazolium, polyarylalkylene ammonium, polyarylalkylene diammonium, polyarylalkylene pyrrolinium, polyarylalkylene imidazolium, polyarylalkylene pyrazolinium, polyarylalkylene oxazolinium, polyarylalkylene thiazolinium, polyarylalkylene pyridinium, polyarylalkylene pyrimidinium, polyarylalkylene pyrazinium, polyarylalkylene pyrazidimium, polyarylalkylene thiazinium, polyarylalkylene morpholinium, polyarylalkylene piperidinium, polyarylalkylene piperidinium, polyarylalkylene pyrrolidinium, polyarylalkylene triphenylphosphonium, polyarylalkylene trimethylphosphonium, polyarylalkylene triethylphosphonium, polyarylalkylene tripropylphosphonium, polyarylalkylene tributylphosphonium, polyarylalkylene trichlorophosphonium, polyarylalkylene trifluorophosphonium, and polyarylalkylene diazolium can be selected from.

[0182] The cationic polymer main chain is, for example, F - , Cl - , Br - , I- , NO 2 - , NO 3 - , SO 4 2- , R 7 SO 4 - , R 7 CO 2 - , PO 4 2- , R 7 PO 3 - , and R 7 PO 2 - capable of binding to one or more anions including, where R 7 is selected from hydrogen, C 1~4 alkyl, and C 1~4 heteroalkyl. In one embodiment, the anions are each Cl - , Br - 、 I - , HSO 4 - , HCO 2 - , CH 3 CO 2 - , and NO 3 - can be selected from. In other embodiments, the anions are each acetate ions. In other embodiments, the anions are each bisulfate ions. In other embodiments, the anions are each chloride ions. In other embodiments, X is nitrate ion.

[0183] In other embodiments of the polymer catalyst, the polymer backbone is alkylene imidazolium, which is related to the alkylene moiety where one or more of the methylene units of the alkylene moiety are replaced by imidazolium. In one embodiment, the polymer backbone is selected from polyethylene imidazolium, polypropylene imidazolium, and polybutylene imidazolium. In other embodiments of the polymer backbone, when a nitrogen-containing cationic group or a phosphorus-containing cationic group follows the term "alkylene", it is further understood that one or more of the methylene units of the alkylene moiety are substituted by the nitrogen-containing cationic group or the phosphorus-containing cationic group.

[0184] In other embodiments, the monomers having heteroatoms can form polymers in combination with one or more difunctionalized compounds such as dihaloalkanes, di(alkylsulfonyloxy)alkanes, and di(arylsulfonyloxy)alkanes. The monomers have at least two heteroatoms for linking with the difunctionalized alkane to form polymer chains. These difunctionalized compounds can be further substituted as described herein. In some embodiments, the difunctionalized compound(s) is 1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, 1,2-dichlorobutane, 1,3-dichlorobutane, 1,4-dichlorobutane, 1,2-dichloropentane, 1,3-dichloropentane, 1,4-dichloropentane, 1,5-dichloropentane, 1,2-dibromoethane, 1,2-dibromopropane, 1,3-dibromopropane, 1,2-dibromobutane, 1,3-dibromobutane, 1,4-dibromobutane, 1,2-dibromopentane, 1,3-dibromopentane, 1,4-dibromopentane, 1,5-dibromopentane, 1,2-diiodoethane, 1,2-diiodopropane, 1,3-diiodopropane, 1,2-diiodobutane, 1,3-diiodobutane, 1,4-diiodobutane, 1,2-diiodopentane, 1,3-diiodopentane, 1,4-diiodopentane, 1,5-diiodopentane, 1,2-dimethanesulfoxyethane, 1,2-dimethanesulfoxypropane, 1,3-dimethanesulfoxypropane, 1,2-dimethanesulfoxybutane, 1,3-dimethanesulfoxybutane, 1,4-dimethanesulfoxybutane, 1,2-dimethanesulfoxypentane, 1,3-dimethanesulfoxypentane, 1,4-dimethanesulfoxypentane, 1,5-dimethanesulfoxypentane, 1,2-diethanesulfoxyethane, 1,2-diethanesulfoxypropane, 1,3-diethanesulfoxypropane, 1,2-diethanesulfoxybutane, 1,3-diethanesulfoxybutane, 1,4-diethanesulfoxybutane, 1,2-diethanesulfoxypentane, 1,3-diethanesulfoxypentane, 1,4-diethanesulfoxypentane, 1,5-diethanesulfoxypentane, 1,2-dibenzene sulfoxyethane, 1,2-dibenzene sulfoxypropane, 1,It can be selected from 3-dibenzene sulfoxypropane, 1,2-dibenzene sulfoxybutane, 1,3-dibenzene sulfoxybutane, 1,4-dibenzene sulfoxybutane, 1,2-dibenzene sulfoxypentane, 1,3-dibenzene sulfoxypentane, 1,4-dibenzene sulfoxypentane, 1,5-dibenzene sulfoxypentane, 1,2-di-p-toluenesulfoxyethane, 1,2-di-p-toluenesulfoxypropane, 1,3-di-p-toluenesulfoxypropane, 1,2-di-p-toluenesulfoxybutane, 1,3-di-p-toluenesulfoxybutane, 1,4-di-p-toluenesulfoxybutane, 1,2-di-p-toluenesulfoxypentane, 1,3-di-p-toluenesulfoxypentane, 1,4-di-p-toluenesulfoxypentane, and 1,5-di-p-toluenesulfoxypentane.,

[0185] Furthermore, the number of atoms between side chains in the polymer main chain can be changed. In some embodiments, there are 0 to 20 atoms, 0 to 10 atoms, 0 to 6 atoms, or 0 to 3 atoms between side chains attached to the polymer main chain.,

[0186] In some embodiments, the polymer can be a homopolymer having at least two monomer units, where all the units contained in the polymer are derived from the same monomer in the same manner. In other embodiments, the polymer can be a heteropolymer having at least two monomer units, where at least one monomer unit contained in the polymer is different from the other monomer units in the polymer. The different monomer units in the polymer can be in a random order, an alternating arrangement of any length of a given monomer, or blocks of monomers.,

[0187] Other exemplary polymers include, for example, those containing a polyalkylene backbone substituted with one or more groups selected from hydroxyl, carboxylic acid, unsubstituted and substituted phenyl, halide, unsubstituted and substituted amine, unsubstituted and substituted ammonia, unsubstituted and substituted pyrrole, unsubstituted and substituted imidazole, unsubstituted and substituted pyrazole, unsubstituted and substituted oxazole, unsubstituted and substituted thiazole, unsubstituted and substituted pyridine, unsubstituted and substituted pyrimidine, unsubstituted and substituted pyrazine, unsubstituted and substituted pyrazidine, unsubstituted and substituted thiadiazine, unsubstituted and substituted morpholine, unsubstituted and substituted piperidine, unsubstituted and substituted piperidine, unsubstituted and substituted pyrrolidine, unsubstituted and substituted triphenyl phosphonate, unsubstituted and substituted trimethyl phosphonate, unsubstituted and substituted triethyl phosphonate, unsubstituted and substituted tripropyl phosphonate, unsubstituted and substituted tributyl phosphonate, unsubstituted and substituted trichloro phosphonate, unsubstituted and substituted trifluoro phosphonate, and unsubstituted and substituted diazole.

[0188] In the case of the polymers described herein, multiple nomenclature rules are well recognized in the art. For example, a polyethylene backbone (-CH 2 -CH(phenyl)-CH 2 -CH(phenyl)-) having a direct bond to an unsubstituted phenyl group is also known as polystyrene. If the phenyl group is substituted by an ethenyl group, the polymer can be named polydivinylbenzene (-CH 2 -CH(4-vinylphenyl)-CH 2 -CH(4-vinylphenyl)-). Further examples of heteropolymers can include those that are functionalized after polymerization.

[0189] One suitable example is polystyrene-co-divinylbenzene: (-CH 2 -CH(phenyl)-CH 2 -CH(4-ethylenephenyl)-CH 2 -CH(phenyl)-CH 2-CH(4-vinylphenyl)-). Here, the ethenyl functional group can be present at the 2-, 3- or 4-position on the phenyl ring.

[0190] Referring to FIG. 12, in yet another embodiment, the polymer backbone is a polyalkylene imidazolium.

[0191] Furthermore, the number of atoms between the side chains in the polymer backbone can be varied. In some embodiments, there are 0 to 20 atoms, 0 to 10 atoms, or 0 to 6 atoms, or 0 to 3 atoms between the side chains attached to the polymer backbone. Referring to FIG. 10, in one embodiment, there are 3 carbon atoms between the side chain having a Bronsted-Lowry acid and the side chain having a cationic group. In another example, referring to FIG. 11, there are no atoms between the side chain having an acidic site and the side chain having an ionic site.

[0192] Solid Particles for Polymer Catalysts The polymer catalysts described herein can form solid particles. One of ordinary skill in the art would likely recognize various known techniques and methods for making solid particles from the polymers described herein. For example, the solid particles can be formed by emulsion polymerization or dispersion polymerization procedures known to those skilled in the art. In other embodiments, the solid particles can be formed by grinding or breaking the polymer into particles, which is also a technique and method known to those skilled in the art. Methods known in the art for preparing solid particles include coating the surface of a solid core with the polymers described herein. Suitable materials for the solid core can include inert materials (e.g., aluminum oxide, corn cobs, ground glass, shredded plastic, pumice, silicon carbide or walnut shells) or magnetic materials. The core particles coated with the polymer can be made by dispersion polymerization to grow a crosslinked polymer shell around the core material, or by spray coating methods or melt methods.

[0193] Other methods known in the art for preparing solid particles include the step of coating the polymers described herein on the surface of a solid core. The solid core can be a non-catalytic carrier. Substances suitable for the solid core can include inert substances (e.g., aluminum oxide, corn cobs, crushed glass, shredded plastic, pumice, silicon carbide, or walnut shells) or magnetic materials. In one embodiment of the polymer catalyst, the solid core is composed of iron. The core particles coated with the polymer can be prepared by techniques and methods known to those skilled in the art, for example, by dispersion polymerization to grow a cross-linked polymer shell around the core material, or by spray coating methods or melting methods.

[0194] The polymer catalyst particles supported on a solid can have a solid core with the polymer coated on the surface of the solid core. In some embodiments, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, or at least about 50% of the catalytic activity of the solid particles can be present on or near the outer surface of the solid particles. In some embodiments, the solid core can have an inert substance or a magnetic material. In one embodiment, the solid core is composed of iron.

[0195] The solid particles coated with the polymers described herein have one or more catalytic properties. In some embodiments, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% of the catalytic activity of the solid particles is present on or near the outer surface of the solid particles.

[0196] In some embodiments, the solid particles substantially do not contain pores and have, for example, pores of about 50% or less, about 40% or less, about 30% or less, about 20% or less, about 15% or less, about 10% or less, about 5% or less, or about 1% or less. The porosity can be measured by methods well known in the art. For example, the Brunauer-Emmett-Teller (BET) surface area is determined (measured) using the adsorption of nitrogen gas on the internal and external surfaces of the substance (Brunauer, S. et al., J. Am. Chem. Soc., 1938, 60: 309). Other methods include measuring the solvent retention rate by exposing the substance to a suitable solvent (such as water) and then thermally removing the solvent to measure the volume of the internal pores. Other solvents suitable for measuring the porosity of the polymer catalyst include polar solvents such as DMF, DMSO, acetone, and alcohol.

[0197] In other embodiments, the solid particles include a microporous gel resin. In still other embodiments, the solid particles include a macroporous gel resin.

[0198] Carrier of the solid-supported catalyst In certain embodiments of the solid-supported catalyst, the carrier can be selected from biochar, carbon, amorphous carbon, activated carbon, silica, silica gel, alumina, magnesia, titania, zirconia, clay (e.g., kaolinite), magnesium silicate, silicon carbide, zeolite (e.g., mordenite), ceramics, and any combination thereof. In one embodiment, the carrier is carbon. The carrier for the carbon carrier can be biochar, amorphous carbon, or activated carbon. In one embodiment, the carrier is activated carbon.

[0199] The carbon carrier is 0.01 - 50 m 2It can have a surface area of the dry matter per g. The carbon carrier can have a density of 0.5 to 2.5 kg / L. The carrier can be characterized using any suitable instrumental analysis method or technique known in the art, including, for example, scanning electron microscopy (SEM), powder X-ray diffraction (XRD), Raman spectroscopy, and Fourier transform infrared spectroscopy (FTIR). The carbon carrier can be prepared from carbonaceous materials including, for example, shrimp shells, chitin, coconut shells, wood pulp, pulp for papermaking, cotton, cellulose, hardwood, softwood, wheat straw, sugarcane bagasse, cassava stems, corn stover, oil palm residues, bitumen, asphaltum, tar, coal, pitch, and any combination thereof. Those skilled in the art will recognize appropriate methods for preparing the carbon carriers used herein. See, for example, M. Inagaki, L.R. Radovic, Carbon, Vol. 40, p. 2263 (2002), or A.G. Pandolfo and A.F. Hollenkamp, "Review: Carbon Properties and their role in supercapacitors", Journal of Power Sources, Vol. 157, pp. 11 - 27 (2006).

[0200] In other embodiments, the carrier is silica, silica gel, alumina, or silica - alumina. Those skilled in the art will recognize appropriate methods for preparing these silica - or alumina - based solid carriers used herein. See, for example, Catalyst supports and supported catalysts by A.B. Stiles, Butterworth Publishers, Stoneham MA, 1987.

[0201] In yet other embodiments, the carrier is a combination of a carbon carrier and one or more other carriers selected from silica, silica gel, alumina, magnesia, titania, zirconia, clay (e.g., kaolinite), magnesium silicate, silicon carbide, zeolite (e.g., mordenite), and ceramics.

[0202] Definition A "Bronsted-Lowry acid" refers to a neutral or ionic form of a molecule, or a substituent thereof, that can donate a proton (hydrogen cation, H + +).

[0203] A "homopolymer" refers to a polymer having at least two monomer units, wherein all units contained within the polymer are derived from the same monomer. One suitable example is polyethylene, in which ethylene monomers are linked to form a repeating chain (-CH 2 -CH 2 -CH 2 -). Another suitable example is polyvinyl chloride having the structure (-CH 2 -CHCl-CH 2 -CHCl-), wherein the repeating unit of -CH 2 -CHCl- is derived from the H 2 C=CHCl monomer.

[0204] A "heteropolymer" refers to a polymer having at least two monomer units, wherein at least one monomer unit is different from the other monomer units in the polymer. Heteropolymers also refer to polymers having difunctional or trifunctional monomer units that can be incorporated into the polymer in different ways. The different monomer units in the polymer can be in a random order, an alternating arrangement of any length of a given monomer, or blocks of monomers. One suitable example is polyethylene imidazolium, which can be the polymer illustrated in FIG. 12 in the case of an alternating arrangement. Another suitable example is polystyrene-co-divinylbenzene, which in the case of an alternating arrangement is (-CH 2 -CH(phenyl)-CH 2 -CH(4-ethylphenyl)-CH 2 -CH(phenyl)-CH 2-CH(4-vinylphenyl)-). Here, the vinyl functional group can be present at the 2-, 3- or 4-position on the phenyl ring.

[0205] As used herein,

[0206]

Chemical formula

[0207] When ranges of values are recited, each value and sub-range within the range is intended to be included. For example, "C 1~6 alkyl" (which can also be referred to as 1-6C alkyl, C1-C6 alkyl, or C1-6 alkyl) includes C 1 C 2 C 3 C 4 C 5 C 6 C 1~6 C 1~5 C 1~4 C 1~3 C 1~2 C 2~6 C 2~5 C 2~4 C 2~3 C 3~6 C 3~5 C 3~4 C 4~6 C 4~5 and C 5~6 alkyl and is intended to be included.

[0208] "Alkyl", when unsubstituted, includes monovalent straight-chain or branched saturated hydrocarbon groups containing only C and H. In some embodiments, alkyl, as used herein, has 1 to 10 carbon atoms (e.g., C 1~10 alkyl), 1 to 6 carbon atoms (e.g., C 1~6 alkyl), or 1 to 3 carbon atoms (e.g., C 1~3It can have an alkyl group. Representative linear alkyl groups include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl. Representative branched alkyl groups include, for example, isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, 2-methylbutyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, and 2,3-dimethylbutyl. When an alkyl residue having a specific number of carbons is named, it is intended to be described including all geometric isomers having that number of carbons. Thus, for example, "butyl" is intended to include n-butyl, sec-butyl, iso-butyl, and tert-butyl, and "propyl" is intended to include n-propyl and iso-propyl..

[0209] "Alkoxy" refers to an -O-alkyl group bonded to the parent structure through an oxygen atom. Examples of alkoxy can include methoxy, ethoxy, propoxy, and isopropoxy. In some embodiments, alkoxy, as used herein, has 1 to 6 carbon atoms (e.g., O-(C 1~6 alkyl)), or 1 to 4 carbon atoms (e.g., O-(C 1~4 alkyl)).

[0210] "Alkenyl", when unsubstituted, refers to a monovalent straight-chain or branched hydrocarbon group containing only C and H and containing at least one double bond. In some embodiments, alkenyl has 2 to 10 carbon atoms (e.g., C 2~10 alkenyl), or 2 to 5 carbon atoms (e.g., C 2~5 alkenyl). When an alkenyl residue having a specific number of carbons is named, it is intended to be described including all geometric isomers having that number of carbons. Thus, for example, "butenyl" is intended to include n-butenyl, sec-butenyl, and iso-butenyl. Examples of alkenyl include -CH=CH 2 , -CH 2 -CH=CH 2and -CH 2 -CH=CH-CH=CH 2 may be included. One or more carbon-carbon double bonds can be internal (e.g., in 2-butenyl) or terminal (e.g., in 1-butenyl). C 2~4 Examples of alkenyl groups include ethenyl (C2), 1-propenyl (C3), 2-propenyl (C3), 1-butenyl (C4), 2-butenyl (C4), and butadienyl (C4). C 2~6 Examples of alkenyl groups include the above-mentioned C 2~4 alkenyl groups, as well as pentenyl (C5), pentadienyl (C5), and hexenyl (C6). Additional examples of alkenyl include heptenyl (C7), octenyl (C8), and octatrieneyl (C8).

[0211] "Alkynyl", when unsubstituted, refers to a monovalent straight-chain or branched hydrocarbon group containing C and H and containing at least one triple bond. In some embodiments, alkynyl has 2 to 10 carbon atoms (e.g., C 2~10 alkynyl), or 2 to 5 carbon atoms (e.g., C 2~5 alkynyl). When an alkynyl residue having a specific number of carbons is named, it is intended to be described as encompassing all geometric isomers having that number of carbons. Thus, for example, "pentynyl" is intended to include n-pentynyl, sec-pentynyl, iso-pentynyl, and tert-pentynyl. Examples of alkynyl may include -C≡CH or -C≡C-CH 3 may be included.

[0212] In some embodiments, alkyl, alkoxy, alkenyl, and alkynyl may each independently be unsubstituted or substituted with one or more substituents. In certain embodiments, substituted alkyl, substituted alkoxy, substituted alkenyl, and substituted alkynyl may each independently have from 1 to 5 substituents, from 1 to 3 substituents, from 1 to 2 substituents, or 1 substituent per occurrence. Examples of alkyl, alkoxy, alkenyl, and alkynyl substituents can include alkoxy, cycloalkyl, aryl, aryloxy, amino, amide, carbamate, carbonyl, oxo (=O), heteroalkyl (e.g., ether), heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, and thio. In certain embodiments, one or more substituents of substituted alkyl, alkoxy, alkenyl, and alkynyl are independently cycloalkyl, aryl, heteroalkyl (e.g., ether), heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, oxo, -OR a ,-N(R a ) 2 ,-C(O)N(R a ) 2 ,-N(R a )C(O)R a ,-C(O)R a ,-N(R a )S(O) t R a (where t is 1 or 2),-SR a , and -S(O) t N(R a ) 2 (where t is 1 or 2) and are independently selected from. In certain embodiments, each R a is independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl (e.g., attached through a ring carbon), -C(O)R' and -S(O) tR' (where t is 1 or 2), where each R' is independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl. In one embodiment, R a is independently hydrogen, alkyl, haloalkyl, cycloalkyl, aryl, aralkyl (e.g., alkyl substituted by aryl bonded to the parent structure via an alkyl group), heterocycloalkyl or heteroaryl.

[0213] "Heteroalkyl", "heteroalkenyl" and "heteroalkynyl" each contain an alkyl group, an alkenyl group and an alkynyl group, where one or more atoms of the backbone chain are selected from atoms other than carbon, such as oxygen, nitrogen, sulfur, phosphorus, or any combination thereof. For example, heteroalkyl can be an ether in which at least one of the carbon atoms in the alkyl group is replaced by an oxygen atom. A numerical range can be given (e.g., C 1~4 heteroalkyl), which refers to the total chain length, which in this example is 4 atom lengths. For example, -CH 2 OCH 2 CH 3 group is called "C 4 " heteroalkyl, which includes the heteroatom center in the description of the atomic chain length. The linkage to the rest of the parent structure can, in one embodiment, be through a heteroatom, or, in another embodiment, through a carbon atom in the heteroalkyl chain. Heteroalkyl groups include, for example, methoxyethanyl (-CH 2 CH 2 OCH 3 ), ethoxymethanyl (-CH 2 OCH 2 CH 3 ), (methoxymethoxy)ethanyl (-CH 2 CH 2 OCH 2 OCH 3 ), (methoxymethoxy)methanyl (-CH 2 OCH 2 OCH 3and (methoxyethoxy)methyl (-CH 2 OCH 2 CH 2 OCH 3 ), etc. of ethers, -CH 2 CH 2 NHCH 3、 -CH 2 CH 2 N(CH 3 ) 2、 -CH 2 NHCH 2 CH 3 , and -CH 2 N(CH 2 CH 3 )(CH 3 ) etc. of amines may be included. In some embodiments, heteroalkyl, heteroalkenyl, or heteroalkynyl may be unsubstituted or substituted with one or more substituents. In certain embodiments, substituted heteroalkyl, heteroalkenyl, or heteroalkynyl can have 1 to 5 substituents, 1 to 3 substituents, 1 to 2 substituents, or 1 substituent. Examples of heteroalkyl, heteroalkenyl, or heteroalkynyl substituents can include the substituents described above for alkyl.

[0214] "Carbocyclic" can include cycloalkyl, cycloalkenyl or cycloalkynyl. "Cycloalkyl" refers to a monocyclic or polycyclic alkyl group. "Cycloalkenyl" refers to a monocyclic or polycyclic alkenyl group (e.g., containing at least one double bond). "Cycloalkynyl" refers to a monocyclic or polycyclic alkynyl group (e.g., containing at least one triple bond). Cycloalkyl, cycloalkenyl, or cycloalkynyl can consist of one ring such as cyclohexyl, or multiple rings such as adamantyl. Cycloalkyl, cycloalkenyl, or cycloalkynyl having two or more rings can be fused, spiro or bridged, or a combination thereof. In some embodiments, cycloalkyl, cycloalkenyl, and cycloalkynyl have 3 to 10 ring atoms (i.e., C 3 ~C 10Cycloalkyl, C 3 ~C 10 Cycloalkenyl, and C 3 ~C 10 Cycloalkynyl), 3 to 8 ring atoms (e.g., C 3 ~C 8 Cycloalkyl, C 3 ~C 8 Cycloalkenyl, and C 3 ~C 8 Cycloalkynyl), or 3 to 5 ring atoms (i.e., C 3 ~C 5 Cycloalkyl, C 3 ~C 5 Cycloalkenyl, and C 3 ~C 5 Cycloalkynyl) is included. In certain embodiments, the cycloalkyl, cycloalkenyl, or cycloalkynyl is heteroatom-free and includes bridged and spiro-fused cyclic structures. In other embodiments, the cycloalkyl, cycloalkenyl, or cycloalkynyl includes monocyclic or fused polycyclic (i.e., rings sharing an adjacent pair of ring atoms) groups. C 3-6 The carbocyclic group may include, for example, cyclopropyl (C 3 ), cyclobutyl (C 4 ), cyclopentyl (C 5 ), cyclopentenyl (C 5 ), cyclohexyl (C 6 ), cyclohexenyl (C 6 ), and cyclohexadienyl (C 6 ). C 3~8 The carbocyclic group may include, for example, the above-described C 3~6 carbocyclic group, and cycloheptyl (C 7 ), cycloheptadienyl (C 7 ), cycloheptatrieneyl (C 7 ), cyclooctyl (C 8 ), bicyclo[2.2.1]heptanyl, and bicyclo[2.2.2]octanyl. C 3~10 The carbocyclic group may include, for example, the above-described C 3~8A carbocyclic group, as well as octahydro-1H-indenyl, decahydronaphthalenyl, and spiro[4.5]decanyl may be included.

[0215] "Heterocyclyl" refers to the above-mentioned carbocyclyl having one or more ring heteroatoms independently selected from nitrogen, oxygen, phosphorus, and sulfur. Heterocyclyl may include, for example, heterocycloalkyl, heterocycloalkenyl, and heterocycloalkynyl. In some embodiments, heterocyclyl is a 3- to 18-membered non-aromatic monocyclic or polycyclic moiety having at least one heteroatom selected from nitrogen, oxygen, phosphorus, and sulfur. In certain embodiments, heterocyclyl can be monocyclic or polycyclic (e.g., bicyclic, tricyclic, or tetracyclic), where the polycyclic ring system can be a fused, bridged, or spiro ring system. The heterocyclyl polycyclic ring system can contain one or more heteroatoms in one or both rings.

[0216] The N-containing heterocyclyl moiety refers to a non-aromatic group in which at least one of the skeletal atoms of the ring is a nitrogen atom. The heteroatom(s) in the heterocyclyl group may optionally be oxidized. One or more nitrogen atoms, if present, may optionally be quaternized. In certain embodiments, heterocyclyl can also include a ring system substituted by one or more oxide (-O-) substituents such as piperidinyl N-oxide. Heterocyclyl is attached to the structure of the parent molecule through any atom of the ring(s).

[0217] In some embodiments, the heterocyclyl is also a ring system having one or more fused carbocyclic groups, aryl groups or heteroaryl groups, wherein the point of attachment is in either the carbocyclic ring or the heterocyclic ring. In some embodiments, the heterocyclyl is a 5- to 10-membered non-aromatic ring system having ring carbon atoms and 1 to 4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen and sulfur (e.g., 5- to 10-membered heterocyclyl). In some embodiments, the heterocyclyl group is a 5- to 8-membered non-aromatic ring system having ring carbon atoms and 1 to 4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen and sulfur (e.g., 5- to 8-membered heterocyclyl). In some embodiments, the heterocyclyl group is a 5- to 6-membered non-aromatic ring system having ring carbon atoms and 1 to 4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen and sulfur (e.g., 5- to 6-membered heterocyclyl). In some embodiments, the 5- to 6-membered heterocyclyl has 1 to 3 ring heteroatoms selected from nitrogen, oxygen and sulfur. In some embodiments, the 5- to 6-membered heterocyclyl has 1 to 2 ring heteroatoms selected from nitrogen, oxygen and sulfur. In some embodiments, the 5- to 6-membered heterocyclyl has 1 ring heteroatom selected from nitrogen, oxygen and sulfur.

[0218] "Aryl" refers to an aromatic group having a single ring (e.g., phenyl), multiple rings (e.g., biphenyl), or multiple fused rings (e.g., naphthyl, fluorenyl and anthryl). In some embodiments, aryl, as used herein, has at least one ring having a conjugated pi electron system and has 6 to 10 ring atoms (e.g., C 6 ~C 10 aromatic or C 6 ~C 10It has an aryl group. For example, a divalent group formed from a substituted benzene derivative and having a free valence at a ring atom is named as a substituted phenylene group. In certain embodiments, an aryl having two or more rings, at least one of which is non-aromatic, can be linked to the parent structure at either an aromatic ring position or a non-aromatic ring position. In certain embodiments, the aryl includes a monocyclic or fused polycyclic (i.e., rings sharing a pair of adjacent ring atoms) group.

[0219] "Heteroaryl" refers to an aromatic group having one or more ring heteroatoms independently selected from nitrogen, oxygen, phosphorus, and sulfur, and having a single ring, multiple rings, or multiple fused rings. In some embodiments, the heteroaryl is an aromatic monocyclic or bicyclic ring containing one or more heteroatoms independently selected from nitrogen, oxygen, and sulfur, with the remaining ring atoms being carbon. In certain embodiments, the heteroaryl is a 5- to 18-membered monocyclic or polycyclic (e.g., bicyclic or tricyclic) aromatic ring system (e.g., having 6, 10, or 14 pi electrons shared in the ring array) provided in an aromatic ring system, having ring carbon atoms and 1 to 6 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, phosphorus, and sulfur (e.g., 5- to 18-membered heteroaryl). In certain embodiments, the heteroaryl can have a single ring (e.g., pyridyl, pyridinyl, imidazolyl) or multiple fused rings (e.g., indolizinyl, benzothienyl), and this fused ring may or may not be aromatic. In other embodiments, a heteroaryl having two or more rings, at least one of which is non-aromatic, can be linked to the parent structure at either an aromatic ring position or a non-aromatic ring position. In one embodiment, a heteroaryl having two or more rings, at least one of which is non-aromatic, is linked to the parent structure at an aromatic ring position. The heteroaryl polycyclic ring system can include one or more heteroatoms in one or both rings.

[0220] For example, in one embodiment, an N-containing "heteroaryl" refers to an aromatic group in which at least one of the ring backbone atoms is a nitrogen atom. One or more heteroatoms (one or more) in the heteroaryl group may optionally be oxidized. One or more nitrogen atoms, if present, are optionally quaternized. In other embodiments, heteroaryl can include ring systems substituted with one or more oxide (-O-) substituents, such as pyridinyl N-oxide. Heteroaryl can be attached to the parent molecule through any atom of the ring(s).

[0221] In other embodiments, the heteroaryl can include a ring system having one or more fused aryl groups, where the point of attachment is on either an aryl ring or a heteroaryl ring. In still other embodiments, the heteroaryl can include a ring system having one or more carbocycyl groups or heterocycyl groups, where the point of attachment is on the heteroaryl ring. In the case of a polycyclic heteroaryl group in which one ring does not contain a heteroatom (e.g., indolyl, quinolinyl, and carbazolyl), the point of attachment can be on either ring, i.e., the ring having the heteroatom (e.g., 2-indolyl) or the ring not containing a heteroatom (e.g., 5-indolyl). In some embodiments, the heteroaryl group is a 5- to 10-membered aromatic ring system having ring carbon atoms and 1 to 4 ring heteroatoms provided in an aromatic ring system, where each heteroatom is independently selected from nitrogen, oxygen, phosphorus, and sulfur (e.g., 5- to 10-membered heteroaryl). In some embodiments, the heteroaryl group is a 5- to 8-membered aromatic ring system having ring carbon atoms and 1 to 4 ring heteroatoms provided in an aromatic ring system, where each heteroatom is independently selected from nitrogen, oxygen, phosphorus, and sulfur (e.g., 5- to 8-membered heteroaryl). In some embodiments, the heteroaryl group is a 5- to 6-membered aromatic ring system having ring carbon atoms and 1 to 4 ring heteroatoms provided in an aromatic ring system, where each heteroatom is independently selected from nitrogen, oxygen, phosphorus, and sulfur (e.g., 5- to 6-membered heteroaryl). In some embodiments, the 5- to 6-membered heteroaryl has 1 to 3 ring heteroatoms selected from nitrogen, oxygen, phosphorus, and sulfur. In some embodiments, the 5- to 6-membered heteroaryl has 1 to 2 ring heteroatoms selected from nitrogen, oxygen, phosphorus, and sulfur. In some embodiments, the 5- to 6-membered heteroaryl has 1 ring heteroatom selected from nitrogen, oxygen, phosphorus, and sulfur.

[0222] In some embodiments, a carbocyclyl (e.g., including cycloalkyl, cycloalkenyl or cycloalkynyl), aryl, heteroaryl, and heterocyclyl may each independently be unsubstituted or substituted by one or more substituents. In certain embodiments, a substituted carbocyclyl (e.g., including substituted cycloalkyl, substituted cycloalkenyl or substituted cycloalkynyl), substituted aryl, substituted heteroaryl, substituted heterocyclyl may each independently have 1 to 5 substituents, 1 to 3 substituents, 1 to 2 substituents, or 1 substituent. Examples of carbocyclyl (e.g., including cycloalkyl, cycloalkenyl or cycloalkynyl), aryl, heteroaryl, heterocyclyl substituents include alkyl, alkenyl, alkoxy, cycloalkyl, aryl, heteroalkyl (e.g., ether), heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, oxo (=O), -OR a 、-N(R a ) 2 、-C(O)N(R a ) 2 、-N(R a )C(O)R a 、-C(O)R a 、-N(R a )S(O) t R a (where t is 1 or 2), -SR a 、and -S(O) t N(R a ) 2 (where t is 1 or 2) (R a is as described herein) may be included.

[0223] As used herein, it is understood that any moiety referred to as a "linker" refers to a divalent moiety. Thus, for example, an "alkyl linker" has a divalent but refers to the same residue as alkyl. Examples of alkyl linkers include -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH2 -, and -CH 2 CH 2 CH 2 CH 2 - is included. An "alkenyl linker" has a divalent nature and refers to the same residue as alkenyl. Examples of alkenyl linkers include -CH=CH-, -CH 2 -CH=CH- and -CH 2 -CH=CH-CH 2 - is included. An "alkynyl linker" has a divalent nature and refers to the same residue as alkynyl. Examples of alkynyl linkers include -C≡C- or -C≡C-CH 2 - is included. Similarly, a "carbocyclic linker", an "aryl linker", a "heteroaryl linker", and a "heterocyclic linker" have a divalent nature and refer to the same residues as carbocyclic, aryl, heteroaryl, and heterocyclic, respectively.

[0224] "Amino" or "amine" is -N(R a )(R b ), where R a and R b are each independently selected from hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl (e.g., bonded through a carbon chain), cycloalkyl, aryl, heterocycloalkyl (e.g., bonded through a ring carbon), heteroaryl (e.g., bonded through a ring carbon), -C(O)R' and -S(O) t R' (t is 1 or 2), where R' are each independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl. In one embodiment, it is understood that amino includes amide (e.g., -NR a C(O)R b ). In certain embodiments, R a and R bIt is further understood that the alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl moieties, as described herein, may be further substituted. R a and R b may be the same or different. For example, in one embodiment, amino is -NH 2 (R a and R b are each hydrogen). In other embodiments where R a and R b are other than hydrogen, R a and R b can, together with the nitrogen atom to which they are attached, form a 3-, 4-, 5-, 6-, or 7-membered ring. Such examples can include 1-pyrrolidinyl and 4-morpholinyl.

[0225] "Ammonium" refers to -N(R a )(R b )(R c ) + wherein R a , R b and R c are each independently selected from hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl (e.g., attached via a carbon chain), cycloalkyl, aryl, heterocycloalkyl (e.g., attached via a ring carbon), heteroaryl (e.g., attached via a ring carbon), -C(O)R' and -S(O) t R' (t is 1 or 2), where R' is each independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl, or any two of R a , R b and R c can, together with the atom to which they are attached, form a cycloalkyl, heterocycloalkyl, or any two of R a , R b and R cAny three of them, together with the atoms to which they are attached, can form an aryl or heteroaryl. In certain embodiments, R a , R b and R c Any one or more of alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl moieties may be further substituted as described herein. It is further understood that R a , R b and R c may be the same or different.

[0226] In certain embodiments, "amino" refers to the group -N + (H)(R a )O - , and -N + (R a )(R b )O- N-oxides, where R a and R b are as described herein, where the N-oxide is attached to the parent structure via the N atom. N-oxides can be prepared, for example, by treatment of the corresponding amino group with hydrogen peroxide or m-chloroperbenzoic acid. Those skilled in the art are familiar with the reaction conditions for carrying out N-oxidation.

[0227] "Amide" or "amido" refers to a chemical moiety having the formula -C(O)N(R a )(R b ) or -NR a C(O)R b , where R a and R b are as described herein at each occurrence. In some embodiments, the amide is a C 1~4 amide, which includes the amide carbonyl in the total number of carbons in the group. -C(O)N(R a )(R b ) has R a and R b other than hydrogenWhen present, they can combine with the nitrogen atom to form a 3-membered, 4-membered, 5-membered, 6-membered, or 7-membered ring.

[0228] "Carbonyl" refers to -C(O)R a wherein R a is hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, -N(R') 2 , -S(O) t R', wherein each R' is independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl, and t is 1 or 2. In certain embodiments where each R' is other than hydrogen, the two R' moieties can combine with the nitrogen atom to which they are attached to form a 3-membered, 4-membered, 5-membered, 6-membered, or 7-membered ring. In one embodiment, it is understood that the carbonyl includes an amide (e.g., -C(O)N(R a )(R b )).

[0229] "Carbamate" refers to either of the following groups: -O-C(=O)-N(R a )(R b ) and -N(R a )-C(=O)-OR b (wherein R a and R b are as described herein for each occurrence).

[0230] "Cyano" refers to the -CN group.

[0231] "Halo", "halide", or otherwise "halogen" means fluoro, chloro, bromo or iodo. The terms "haloalkyl", "haloalkenyl", "haloalkynyl" and "haloalkoxy" include the above alkyl, alkenyl, alkynyl and alkoxy moieties where one or more hydrogen atoms are replaced by halo. For example, when a residue is substituted with two or more halo groups, this residue can be named by using a prefix corresponding to the number of attached halo groups. For example, dihaloaryl, dihaloalkyl, and trihaloaryl refer to aryl and alkyl substituted with two ("di") or three ("tri") halo groups, and these groups may, but need not, have the same halogen. Thus, for example, 3,5-difluorophenyl, 3-chloro-5-fluorophenyl, 4-chloro-3-fluorophenyl, and 3,5-difluoro-4-chlorophenyl are within the scope of dihaloaryl. Other examples of haloalkyl groups include difluoromethyl (-CHF 2 ), trifluoromethyl (-CF 3 ), 2,2,2-trifluoroethyl, and 1-fluoromethyl-2-fluoroethyl. The alkyl, alkenyl, alkynyl and alkoxy groups of haloalkyl, haloalkenyl, haloalkynyl and haloalkoxy may each be optionally substituted as defined herein. "Perhaloalkyl" refers to an alkyl or alkylene group in which all hydrogen atoms are replaced by halogen (e.g., fluoro, chloro, bromo, or iodo). In some embodiments, all hydrogen atoms are each replaced by fluoro. In some embodiments, all hydrogen atoms are each replaced by chloro. Examples of perhaloalkyl groups include -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CCl 3 , -CFCl 2 , and -CF 2 Cl.

[0232] "Thio" refers to -SR a wherein R a is as described herein. "Thiol" refers to the group -R a SH, where R a is as described herein.

[0233] "Sulfinyl" refers to -S(O)R a In some embodiments, sulfinyl is -S(O)N(R a )(R b ). "Sulfonyl" refers to -S(O 2 )R a In some embodiments, sulfonyl is -S(O 2 )N(R a )(R b ) or -S(O 2 )OH. For each of these moieties, it is understood that R a and R b are as described herein.

[0234] "Moiety" refers to a particular part or functional group of a molecule. A chemical moiety is often recognized as a chemical entity incorporated into or attached to a molecule.

[0235] As used herein, the term "unsubstituted" means, with respect to a carbon atom, that there are only hydrogen atoms other than the valence atoms connecting the atom to the parent molecular group. One example is propyl (-CH 2 -CH 2 -CH 3 ). In the case of a nitrogen atom, the valence atoms not connecting the atom to the parent molecular group are either hydrogen or an electron pair. In the case of a sulfur atom, the valence atoms not connecting the atom to the parent molecular group are either hydrogen, oxygen, or an electron pair (one or more pairs).

[0236] As used herein, the term "substituted" or "substitution" means that at least one hydrogen present on a radical (e.g., a carbon atom or a nitrogen atom) has been replaced by an acceptable substituent, e.g., a substituent that, upon replacing hydrogen, results in a stable compound, i.e., a compound that does not undergo spontaneous transformation, e.g., by rearrangement, cyclization, elimination, or other reactions. Unless otherwise indicated, a "substituted" radical can have substituents at one or more of the substitutable positions of the radical, and when two or more positions in any given structure are substituted, the substituents can be the same or different at each position. Substituents individually include one or more radicals, and are independently selected from alkyl, alkenyl, alkoxy, cycloalkyl, aryl, heteroalkyl (e.g., ether), heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, oxo (=O), -OR a 、-N(R a ) 2 、-C(O)N(R a ) 2 、-N(R a )C(O)R a 、-C(O)R a 、-N(R a )S(O) t R a (where t is 1 or 2), -SR a and -S(O) t N(R a ) 2 (where t is 1 or 2) (R a is as described herein).

[0237] When substituents are specified by their conventional chemical formulas written from left to right, they equally encompass chemically identical substituents obtained from the structure written from right to left (e.g., -CH 2 O- is equivalent to -OCH 2 -).

[0238] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.

[0239] As used in this specification and the claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise.

[0240] As used herein, references to "about" a value or parameter include (and describe) embodiments that are directed to that value or parameter itself. For example, a description that refers to "about x" includes a description of "x" itself. In other instances, the term "about" refers to a variable of ±0.1% to ±15% of the recited number when used in connection with other measured values or when used to modify a value, unit, constant value, or range of values. For example, in one variation, "about 1" refers to a range of 0.85 to 1.15.

[0241] As used herein, references to "between" two values or parameters include (and describe) embodiments that are directed to those two values or parameters themselves. For example, a description that refers to "between x and y (x~y)" includes a description of "x" and "y" themselves.

[0242] Representative examples of catalysts The polymer catalyst and the solid-supported catalyst can be understood to include any of the Bronsted-Lowry acids, cationic groups, counterions, linkers, hydrophobic groups, crosslinking groups, and polymer backbones or solid supports (as appropriate) described herein, as if every combination were individually enumerated. For example, in one embodiment, the catalyst can include benzenesulfonic acid (i.e., sulfonic acid having a phenyl linker) linked to a polystyrene backbone or bonded to a solid support, and imidazolium chloride directly linked to the polystyrene backbone or directly bonded to the solid support. In another embodiment, the polymer catalyst can include boronyl-benzyl-pyridinium chloride (i.e., boric acid and pyridinium chloride in the same monomer unit having a phenyl linker) linked to a polystyrene backbone or bonded to a solid support. In yet another embodiment, the catalyst can include benzenesulfonic acid and imidazolium sulfate, each individually linked to a polyvinyl alcohol backbone or individually bonded to a solid support.

[0243] In some embodiments, the polymer catalyst is Poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene]; Poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium bisulfate-co-divinylbenzene]; Poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium acetate-co-divinylbenzene]; Poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium nitrate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium bisulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium acetate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium nitrate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium iodide-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium bromide-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium bisulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium acetate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzimidazol-1-ium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzimidazol-1-ium bisulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzimidazol-1-ium acetate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzimidazol-1-ium formate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium-chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium-bisulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium-acetate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium-nitrate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium-chloride-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium bisulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium-bromide-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium bisulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium-iodide-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium bisulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium bisulfate-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium bisulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium acetate-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium bisulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-ium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-ium bisulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-ium acetate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-ium formate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-triphenyl-(4-vinylbenzyl)-phosphonium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-triphenyl-(4-vinylbenzyl)-phosphonium bisulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-triphenyl-(4-vinylbenzyl)-phosphonium acetate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-methyl-1-(4-vinylbenzyl)-piperdin-1-ium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-methyl-1-(4-vinylbenzyl)-piperidin-1-ium bisulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-methyl-1-(4-vinylbenzyl)-piperidin-1-ium acetate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-triethyl-(4-vinylbenzyl)-ammonium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-triethyl-(4-vinylbenzyl)-ammonium bisulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-triethyl-(4-vinylbenzyl)-ammonium acetate-co-divinylbenzene]; Poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-4-boronyl-1-(4-vinylbenzyl)-pyridinium chloride-co-divinylbenzene]; Poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-1-(4-vinylphenyl)methylphosphonic acid-co-divinylbenzene]; Poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium bisulfate-co-1-(4-vinylphenyl)methylphosphonic acid-co-divinylbenzene]; Poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium acetate-co-1-(4-vinylphenyl)methylphosphonic acid-co-divinylbenzene]; Poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium nitrate-co-1-(4-vinylphenyl)methylphosphonic acid-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyl chloride-co-1-methyl-2-vinyl-pyridinium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyl chloride-co-1-methyl-2-vinyl-pyridinium bisulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyl chloride-co-1-methyl-2-vinyl-pyridinium acetate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide-co-divinylbenzene]; Poly[styrene-co-4-vinylphenylphosphonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylphenylphosphonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium bisulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylphenylphosphonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium acetate-co-divinylbenzene]; Poly[styrene-co-3-carboxymethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene]; Poly[styrene-co-3-carboxymethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium bisulfate-co-divinylbenzene]; Poly[styrene-co-3-carboxymethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium acetate-co-divinylbenzene]; Poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene]; Poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium bisulfate-co-divinylbenzene]; Poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium acetate-co-divinylbenzene]; Poly[styrene-co-(4-vinylbenzylamino)-acetic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene]; Poly[styrene-co-(4-vinylbenzylamino)-acetic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium bisulfate-co-divinylbenzene]; Poly[styrene-co-(4-vinylbenzylamino)-acetic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium acetate-co-divinylbenzene]; Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium chloride-co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium chloride-co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium bisulfate-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium bisulfate-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium acetate-co-vinylbenzylmethylmorpholinium acetate-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium acetate-co-vinylbenzylmethylmorpholinium acetate-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylmorpholinium acetate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylmorpholinium acetate-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene) Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium bisulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium nitrate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylmethylimidazolium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylmethylimidazolium bisulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylmethylimidazolium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium bisulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium bisulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene); Poly(butyl-vinylimidazolium chloride-co-butylimidazolium bisulfate-co-4-vinylbenzenesulfonic acid); Poly(butyl-vinylimidazolium bisulfate-co-butylimidazolium bisulfate-co-4-vinylbenzenesulfonic acid); Poly(benzyl alcohol-co-4-vinylbenzyl alcohol sulfonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzyl alcohol); and Poly(benzyl alcohol-co-4-vinylbenzyl alcohol sulfonic acid-co-vinylbenzyltriphenylphosphonium bisulfate-co-divinylbenzyl alcohol) selected from the group consisting of

[0244] In some embodiments, the solid-supported catalyst is Amorphous carbon-supported pyrrolidinium chloride sulfonic acid; Amorphous carbon-supported imidazolium chloride sulfonic acid; Amorphous carbon-supported pyrazolium chloride sulfonic acid; Amorphous carbon-supported oxazolium chloride sulfonic acid; Amorphous carbon-supported thiazolium chloride sulfonic acid; Amorphous carbon-supported pyridinium chloride sulfonic acid; Amorphous carbon-supported pyrimidinium chloride sulfonic acid; Amorphous carbon-supported pyrazinium chloride sulfonic acid; Pyrazidinium chloride sulfonic acid supported on amorphous carbon; Thiazinium chloride sulfonic acid supported on amorphous carbon; Morpholinium chloride sulfonic acid supported on amorphous carbon; Piperidinium chloride sulfonic acid supported on amorphous carbon; Piperidinium chloride sulfonic acid supported on amorphous carbon; Pyrrolidinium chloride sulfonic acid supported on amorphous carbon; Triphenylphosphonium chloride sulfonic acid supported on amorphous carbon; Trimethylphosphonium chloride sulfonic acid supported on amorphous carbon; Triethylphosphonium chloride sulfonic acid supported on amorphous carbon; Tripropylphosphonium chloride sulfonic acid supported on amorphous carbon; Tributylphosphonium chloride sulfonic acid supported on amorphous carbon; Trifluorophosphonium chloride sulfonic acid supported on amorphous carbon; Pyrrolium bromide sulfonic acid supported on amorphous carbon; Imidazolium bromide sulfonic acid supported on amorphous carbon; Pyrazolium bromide sulfonic acid supported on amorphous carbon; Oxazolium bromide sulfonic acid supported on amorphous carbon; Thiazolium bromide sulfonic acid supported on amorphous carbon; Pyridinium bromide sulfonic acid supported on amorphous carbon; Pyrimidinium bromide sulfonic acid supported on amorphous carbon; Pyrazinium bromide sulfonic acid supported on amorphous carbon; Pyrazidimium bromide sulfonic acid supported on amorphous carbon; Thiazinium bromide sulfonic acid supported on amorphous carbon; Morpholinium bromide sulfonic acid supported on amorphous carbon; Piperidinium bromide sulfonic acid supported on amorphous carbon; Amorphous carbon supported piperidinium bromide sulfonic acid; Amorphous carbon supported pyrrolidinium bromide sulfonic acid; Amorphous carbon supported triphenylphosphonium bromide sulfonic acid; Amorphous carbon supported trimethylphosphonium bromide sulfonic acid; Amorphous carbon supported triethylphosphonium bromide sulfonic acid; Amorphous carbon supported tripropylphosphonium bromide sulfonic acid; Amorphous carbon supported tributylphosphonium bromide sulfonic acid; Amorphous carbon supported trifluorophosphonium bromide sulfonic acid; Amorphous carbon supported pyrrolidium bisulfate sulfonic acid; Amorphous carbon supported imidazolium bisulfate sulfonic acid; Amorphous carbon supported pyrazolium bisulfate sulfonic acid; Amorphous carbon supported oxazolium bisulfate sulfonic acid; Amorphous carbon supported thiazolium bisulfate sulfonic acid; Amorphous carbon supported pyridinium bisulfate sulfonic acid; Amorphous carbon supported pyrimidinium bisulfate sulfonic acid; Amorphous carbon supported pyrazinium bisulfate sulfonic acid; Amorphous carbon supported pyrazidimium bisulfate sulfonic acid; Amorphous carbon supported thiazinium bisulfate sulfonic acid; Amorphous carbon supported morpholinium bisulfate sulfonic acid; Amorphous carbon supported piperidinium bisulfate sulfonic acid; Amorphous carbon supported piperidinium bisulfate sulfonic acid; Amorphous carbon supported pyrrolidinium bisulfate sulfonic acid; Amorphous carbon supported triphenylphosphonium bisulfate sulfonic acid; Trimethylphosphonium bisulfate sulfonic acid supported on amorphous carbon; Triethylphosphonium bisulfate sulfonic acid supported on amorphous carbon; Tripropylphosphonium bisulfate sulfonic acid supported on amorphous carbon; Tributylphosphonium bisulfate sulfonic acid supported on amorphous carbon; Trifluorophosphonium bisulfate sulfonic acid supported on amorphous carbon; Pyrrolidinium formate sulfonic acid supported on amorphous carbon; Imidazolium formate sulfonic acid supported on amorphous carbon; Pyrazolium formate sulfonic acid supported on amorphous carbon; Oxazolium formate sulfonic acid supported on amorphous carbon; Thiazolium formate sulfonic acid supported on amorphous carbon; Pyridinium formate sulfonic acid supported on amorphous carbon; Pyrimidinium formate sulfonic acid supported on amorphous carbon; Pyrazinium formate sulfonic acid supported on amorphous carbon; Pyrazidimium formate sulfonic acid supported on amorphous carbon; Thiadinium formate sulfonic acid supported on amorphous carbon; Morpholinium formate sulfonic acid supported on amorphous carbon; Piperidinium formate sulfonic acid supported on amorphous carbon; Piperidinium formate sulfonic acid supported on amorphous carbon; Pyrrolidinium formate sulfonic acid supported on amorphous carbon; Triphenylphosphonium formate sulfonic acid supported on amorphous carbon; Trimethylphosphonium formate sulfonic acid supported on amorphous carbon; Triethylphosphonium formate sulfonic acid supported on amorphous carbon; Tripropylphosphonium formate sulfonic acid supported on amorphous carbon; Tributylphosphonium formate sulfonic acid supported on amorphous carbon; Trifluorophosphonium formate sulfonic acid supported on amorphous carbon; Pyrrolidinium acetate sulfonic acid supported on amorphous carbon; Imidazolium acetate sulfonic acid supported on amorphous carbon; Pyrazolium acetate sulfonic acid supported on amorphous carbon; Oxazolium acetate sulfonic acid supported on amorphous carbon; Thiazolium acetate sulfonic acid supported on amorphous carbon; Pyridinium acetate sulfonic acid supported on amorphous carbon; Pyrimidinium acetate sulfonic acid supported on amorphous carbon; Pyrazinium acetate sulfonic acid supported on amorphous carbon; Pyrazidimium acetate sulfonic acid supported on amorphous carbon; Thiadinium acetate sulfonic acid supported on amorphous carbon; Morpholinium acetate sulfonic acid supported on amorphous carbon; Piperidinium acetate sulfonic acid supported on amorphous carbon; Piperidinium acetate sulfonic acid supported on amorphous carbon; Pyrrolidinium acetate sulfonic acid supported on amorphous carbon; Triphenylphosphonium acetate sulfonic acid supported on amorphous carbon; Trimethylphosphonium acetate sulfonic acid supported on amorphous carbon; Triethylphosphonium acetate sulfonic acid supported on amorphous carbon; Tripropylphosphonium acetate sulfonic acid supported on amorphous carbon; Tributylphosphonium acetate sulfonic acid supported on amorphous carbon; Trifluorophosphonium acetate sulfonic acid supported on amorphous carbon; Pyrrolidinium chloride phosphonic acid supported on amorphous carbon; Imidazolium chloride phosphonic acid supported on amorphous carbon; Pyrazolium chloride phosphonic acid supported on amorphous carbon; Oxazolium chloride phosphonic acid supported on amorphous carbon; Thiazolium chloride phosphonic acid supported on amorphous carbon; Pyridinium chloride phosphonic acid supported on amorphous carbon; Pyrimidinium chloride phosphonic acid supported on amorphous carbon; Pyrazinium chloride phosphonic acid supported on amorphous carbon; Pyrazidimium chloride phosphonic acid supported on amorphous carbon; Thiadinium chloride phosphonic acid supported on amorphous carbon; Morpholinium chloride phosphonic acid supported on amorphous carbon; Piperidinium chloride phosphonic acid supported on amorphous carbon; Piperidinium chloride phosphonic acid supported on amorphous carbon; Pyrrolidinium chloride phosphonic acid supported on amorphous carbon; Triphenylphosphonium chloride phosphonic acid supported on amorphous carbon; Trimethylphosphonium chloride phosphonic acid supported on amorphous carbon; Triethylphosphonium chloride phosphonic acid supported on amorphous carbon; Tripropylphosphonium chloride phosphonic acid supported on amorphous carbon; Tributylphosphonium chloride phosphonic acid supported on amorphous carbon; Trifluorophosphonium chloride phosphonic acid supported on amorphous carbon; Pyrrolium bromide phosphonic acid supported on amorphous carbon; Imidazolium bromide phosphonic acid supported on amorphous carbon; Pyrazolium bromide phosphonic acid supported on amorphous carbon; Oxazolium bromide phosphonic acid supported on amorphous carbon; Thiazolium bromide phosphonic acid supported on amorphous carbon; Pyridinium bromide phosphonic acid supported on amorphous carbon; Amorphous carbon supported pyrimidinium bromide phosphonic acid; Amorphous carbon supported pyrazinium bromide phosphonic acid; Amorphous carbon supported pyrazidimium bromide phosphonic acid; Amorphous carbon supported thiazinium bromide phosphonic acid; Amorphous carbon supported morpholinium bromide phosphonic acid; Amorphous carbon supported piperidinium bromide phosphonic acid; Amorphous carbon supported piperidinium bromide phosphonic acid; Amorphous carbon supported pyrrolidinium bromide phosphonic acid; Amorphous carbon supported triphenylphosphonium bromide phosphonic acid; Amorphous carbon supported trimethylphosphonium bromide phosphonic acid; Amorphous carbon supported triethylphosphonium bromide phosphonic acid; Amorphous carbon supported tripropylphosphonium bromide phosphonic acid; Amorphous carbon supported tributylphosphonium bromide phosphonic acid; Amorphous carbon supported trifluorophosphonium bromide phosphonic acid; Amorphous carbon supported pyrrolinium bisulfate phosphonic acid; Amorphous carbon supported imidazolium bisulfate phosphonic acid; Amorphous carbon supported pyrazolium bisulfate phosphonic acid; Amorphous carbon supported oxazolium bisulfate phosphonic acid; Amorphous carbon supported thiazolium bisulfate phosphonic acid; Amorphous carbon supported pyridinium bisulfate phosphonic acid; Amorphous carbon supported pyrimidinium bisulfate phosphonic acid; Amorphous carbon supported pyrazinium bisulfate phosphonic acid; Amorphous carbon supported pyrazidimium bisulfate phosphonic acid; Amorphous carbon supported thiazinium bisulfate phosphonic acid; Morpholinium bisulfate phosphonic acid supported on amorphous carbon; Piperidinium bisulfate phosphonic acid supported on amorphous carbon; Piperidinium bisulfate phosphonic acid supported on amorphous carbon; Pyrrolidinium bisulfate phosphonic acid supported on amorphous carbon; Triphenylphosphonium bisulfate phosphonic acid supported on amorphous carbon; Trimethylphosphonium bisulfate phosphonic acid supported on amorphous carbon; Triethylphosphonium bisulfate phosphonic acid supported on amorphous carbon; Tripropylphosphonium bisulfate phosphonic acid supported on amorphous carbon; Tributylphosphonium bisulfate phosphonic acid supported on amorphous carbon; Trifluorophosphonium bisulfate phosphonic acid supported on amorphous carbon; Pyrrolinium formate phosphonic acid supported on amorphous carbon; Imidazolium formate phosphonic acid supported on amorphous carbon; Pyrazolium formate phosphonic acid supported on amorphous carbon; Oxazolium formate phosphonic acid supported on amorphous carbon; Thiazolium formate phosphonic acid supported on amorphous carbon; Pyridinium formate phosphonic acid supported on amorphous carbon; Pyrimidinium formate phosphonic acid supported on amorphous carbon; Pyrazinium formate phosphonic acid supported on amorphous carbon; Pyrazidimium formate phosphonic acid supported on amorphous carbon; Thiadinium formate phosphonic acid supported on amorphous carbon; Morpholinium formate phosphonic acid supported on amorphous carbon; Piperidinium formate phosphonic acid supported on amorphous carbon; Piperidinium formate phosphonic acid supported on amorphous carbon; Amorphous carbon supported pyrrolidinium formate phosphonic acid; Amorphous carbon supported triphenylphosphonium formate phosphonic acid; Amorphous carbon supported trimethylphosphonium formate phosphonic acid; Amorphous carbon supported triethylphosphonium formate phosphonic acid; Amorphous carbon supported tripropylphosphonium formate phosphonic acid; Amorphous carbon supported tributylphosphonium formate phosphonic acid; Amorphous carbon supported trifluorophosphonium formate phosphonic acid; Amorphous carbon supported pyrrolinium acetate phosphonic acid; Amorphous carbon supported imidazolium acetate phosphonic acid; Amorphous carbon supported pyrazolium acetate phosphonic acid; Amorphous carbon supported oxazolium acetate phosphonic acid; Amorphous carbon supported thiazolium acetate phosphonic acid; Amorphous carbon supported pyridinium acetate phosphonic acid; Amorphous carbon supported pyrimidinium acetate phosphonic acid; Amorphous carbon supported pyrazinium acetate phosphonic acid; Amorphous carbon supported pyrazidimium acetate phosphonic acid; Amorphous carbon supported thiazinium acetate phosphonic acid; Amorphous carbon supported morpholinium acetate phosphonic acid; Amorphous carbon supported piperidinium acetate phosphonic acid; Amorphous carbon supported piperidinium acetate phosphonic acid; Amorphous carbon supported pyrrolidinium acetate phosphonic acid; Amorphous carbon supported triphenylphosphonium acetate phosphonic acid; Amorphous carbon supported trimethylphosphonium acetate phosphonic acid; Triethylphosphonium acetate phosphonic acid supported on amorphous carbon; Tripropylphosphonium acetate phosphonic acid supported on amorphous carbon; Tributylphosphonium acetate phosphonic acid supported on amorphous carbon; Trifluorophosphonium acetate phosphonic acid supported on amorphous carbon; Ethanoyl-trifosfonium sulfonic acid supported on amorphous carbon; Ethanoyl-methylmorpholinium sulfonic acid supported on amorphous carbon; and Ethanoyl-imidazolium sulfonic acid supported on amorphous carbon selected from the group consisting of.

[0245] In other embodiments, the solid supported catalyst is Pyrrolidinium chloride sulfonic acid supported on activated carbon; Imidazolium chloride sulfonic acid supported on activated carbon; Pyrazolium chloride sulfonic acid supported on activated carbon; Oxazolium chloride sulfonic acid supported on activated carbon; Thiazolium chloride sulfonic acid supported on activated carbon; Pyridinium chloride sulfonic acid supported on activated carbon; Pyrimidinium chloride sulfonic acid supported on activated carbon; Pyrazinium chloride sulfonic acid supported on activated carbon; Pyrazidimium chloride sulfonic acid supported on activated carbon; Thiadinium chloride sulfonic acid supported on activated carbon; Morpholinium chloride sulfonic acid supported on activated carbon; Piperidinium chloride sulfonic acid supported on activated carbon; Piperidinium chloride sulfonic acid supported on activated carbon; Pyrrolidinium chloride sulfonic acid supported on activated carbon; Triphenylphosphonium chloride sulfonic acid supported on activated carbon; Trimethylphosphonium chloride sulfonic acid supported on activated carbon; Triethylphosphonium chloride sulfonic acid supported on activated carbon; Activated carbon supported tripropylphosphonium chloride sulfonic acid; Activated carbon supported tributylphosphonium chloride sulfonic acid; Activated carbon supported trifluorophosphonium chloride sulfonic acid; Activated carbon supported pyrrolidinium bromide sulfonic acid; Activated carbon supported imidazolium bromide sulfonic acid; Activated carbon supported pyrazolium bromide sulfonic acid; Activated carbon supported oxazolium bromide sulfonic acid; Activated carbon supported thiazolium bromide sulfonic acid; Activated carbon supported pyridinium bromide sulfonic acid; Activated carbon supported pyrimidinium bromide sulfonic acid; Activated carbon supported pyrazinium bromide sulfonic acid; Activated carbon supported pyrazidimium bromide sulfonic acid; Activated carbon supported thiazinium bromide sulfonic acid; Activated carbon supported morpholinium bromide sulfonic acid; Activated carbon supported piperidinium bromide sulfonic acid; Activated carbon supported piperidinium bromide sulfonic acid; Activated carbon supported pyrrolidinium bromide sulfonic acid; Activated carbon supported triphenylphosphonium bromide sulfonic acid; Activated carbon supported trimethylphosphonium bromide sulfonic acid; Activated carbon supported triethylphosphonium bromide sulfonic acid; Activated carbon supported tripropylphosphonium bromide sulfonic acid; Activated carbon supported tributylphosphonium bromide sulfonic acid; Activated carbon supported trifluorophosphonium bromide sulfonic acid; Activated carbon supported pyrrolidinium bisulfate sulfonic acid; Activated carbon supported imidazolium bisulfate sulfonic acid; Activated carbon supported pyrazolium bisulfate sulfonic acid; Activated carbon supported oxazolium bisulfate sulfonic acid; Activated carbon supported thiazolium bisulfate sulfonic acid; Activated carbon supported pyridinium bisulfate sulfonic acid; Activated carbon supported pyrimidinium bisulfate sulfonic acid; Activated carbon supported pyrazinium bisulfate sulfonic acid; Activated carbon supported pyrazidimium bisulfate sulfonic acid; Activated carbon supported thiazinium bisulfate sulfonic acid; Activated carbon supported morpholinium bisulfate sulfonic acid; Activated carbon supported piperidinium bisulfate sulfonic acid; Activated carbon supported piperidinium bisulfate sulfonic acid; Activated carbon supported pyrrolidinium bisulfate sulfonic acid; Activated carbon supported triphenylphosphonium bisulfate sulfonic acid; Activated carbon supported trimethylphosphonium bisulfate sulfonic acid; Activated carbon supported triethylphosphonium bisulfate sulfonic acid; Activated carbon supported tripropylphosphonium bisulfate sulfonic acid; Activated carbon supported tributylphosphonium bisulfate sulfonic acid; Activated carbon supported trifluorophosphonium bisulfate sulfonic acid; Activated carbon supported pyrrolium formate sulfonic acid; Activated carbon supported imidazolium formate sulfonic acid; Activated carbon supported pyrazolium formate sulfonic acid; Activated carbon supported oxazolium formate sulfonic acid; Activated carbon supported thiazolium formate sulfonic acid; Activated carbon supported pyridinium formate sulfonic acid; Activated carbon supported pyrimidinium formate sulfonic acid; Activated carbon supported pyrazinium formate sulfonic acid; Activated carbon supported pyrazidimium formate sulfonic acid; Activated carbon supported thiazinium formate sulfonic acid; Activated carbon supported morpholinium formate sulfonic acid; Activated carbon supported piperidinium formate sulfonic acid; Activated carbon supported piperidinium formate sulfonic acid; Activated carbon supported pyrrolidinium formate sulfonic acid; Activated carbon supported triphenylphosphonium formate sulfonic acid; Activated carbon supported trimethylphosphonium formate sulfonic acid; Activated carbon supported triethylphosphonium formate sulfonic acid; Activated carbon supported tripropylphosphonium formate sulfonic acid; Activated carbon supported tributylphosphonium formate sulfonic acid; Activated carbon supported trifluorophosphonium formate sulfonic acid; Activated carbon supported pyrrolinium acetate sulfonic acid; Activated carbon supported imidazolium acetate sulfonic acid; Activated carbon supported pyrazolium acetate sulfonic acid; Activated carbon supported oxazolium acetate sulfonic acid; Activated carbon supported thiazolium acetate sulfonic acid; Activated carbon supported pyridinium acetate sulfonic acid; Activated carbon supported pyrimidinium acetate sulfonic acid; Activated carbon supported pyrazinium acetate sulfonic acid; Activated carbon supported pyrazidimium acetate sulfonic acid; Activated carbon supported thiazinium acetate sulfonic acid; Activated carbon supported morpholinium acetate sulfonic acid; Activated carbon supported piperidinium acetate sulfonic acid; Activated carbon supported piperidinium acetate sulfonic acid; Activated carbon supported pyrrolidinium acetate sulfonic acid; Activated carbon supported triphenylphosphonium acetate sulfonic acid; Activated carbon supported trimethylphosphonium acetate sulfonic acid; Activated carbon supported triethylphosphonium acetate sulfonic acid; Activated carbon supported tripropylphosphonium acetate sulfonic acid; Activated carbon supported tributylphosphonium acetate sulfonic acid; Activated carbon supported trifluorophosphonium acetate sulfonic acid; Activated carbon supported pyrrolidinium chloride phosphonic acid; Activated carbon supported imidazolium chloride phosphonic acid; Activated carbon supported pyrazolium chloride phosphonic acid; Activated carbon supported oxazolium chloride phosphonic acid; Activated carbon supported thiazolium chloride phosphonic acid; Activated carbon supported pyridinium chloride phosphonic acid; Activated carbon supported pyrimidinium chloride phosphonic acid; Activated carbon supported pyrazinium chloride phosphonic acid; Activated carbon supported pyrazidimium chloride phosphonic acid; Activated carbon supported thiazinium chloride phosphonic acid; Activated carbon supported morpholinium chloride phosphonic acid; Activated carbon supported piperidinium chloride phosphonic acid; Activated carbon supported piperidinium chloride phosphonic acid; Activated carbon supported pyrrolidinium chloride phosphonic acid; Activated carbon supported triphenylphosphonium chloride phosphonic acid; Activated carbon supported trimethylphosphonium chloride phosphonic acid; Activated carbon supported triethylphosphonium chloride phosphonic acid; Activated carbon supported tripropylphosphonium chloride phosphonic acid; Activated carbon supported tributylphosphonium chloride phosphonic acid; Activated carbon supported trifluorophosphonium chloride phosphonic acid; Activated carbon supported pyrrolidinium bromide phosphonic acid; Activated carbon supported imidazolium bromide phosphonic acid; Activated carbon supported pyrazolium bromide phosphonic acid; Activated carbon supported oxazolium bromide phosphonic acid; Activated carbon supported thiazolium bromide phosphonic acid; Activated carbon supported pyridinium bromide phosphonic acid; Activated carbon supported pyrimidinium bromide phosphonic acid; Activated carbon supported pyrazinium bromide phosphonic acid; Activated carbon supported pyrazidimium bromide phosphonic acid; Activated carbon supported thiazinium bromide phosphonic acid; Activated carbon supported morpholinium bromide phosphonic acid; Activated carbon supported piperidinium bromide phosphonic acid; Activated carbon supported piperidinium bromide phosphonic acid; Activated carbon supported pyrrolidinium bromide phosphonic acid; Activated carbon supported triphenylphosphonium bromide phosphonic acid; Activated carbon supported trimethylphosphonium bromide phosphonic acid; Activated carbon supported triethylphosphonium bromide phosphonic acid; Activated carbon supported tripropylphosphonium bromide phosphonic acid; Activated carbon supported tributylphosphonium bromide phosphonic acid; Activated carbon supported trifluorophosphonium bromide phosphonic acid; Activated carbon supported pyrrolinium bisulfate phosphonic acid; Activated carbon supported imidazolium bisulfate phosphonic acid; Activated carbon supported pyrazolium bisulfate phosphonic acid; Activated carbon supported oxazolium bisulfate phosphonic acid; Activated carbon supported thiazolium bisulfate phosphonic acid; Activated carbon supported pyridinium bisulfate phosphonic acid; Activated carbon supported pyrimidinium bisulfate phosphonic acid; Activated carbon supported pyrazinium bisulfate phosphonic acid; Activated carbon supported pyrazidimium bisulfate phosphonic acid; Activated carbon supported thiazinium bisulfate phosphonic acid; Activated carbon supported morpholinium bisulfate phosphonic acid; Activated carbon supported piperidinium bisulfate phosphonic acid; Activated carbon supported piperidinium bisulfate phosphonic acid; Activated carbon supported pyrrolidinium bisulfate phosphonic acid; Activated carbon supported triphenylphosphonium bisulfate phosphonic acid; Activated carbon supported trimethylphosphonium bisulfate phosphonic acid; Activated carbon supported triethylphosphonium bisulfate phosphonic acid; Activated carbon supported tripropylphosphonium bisulfate phosphonic acid; Activated carbon supported tributylphosphonium bisulfate phosphonic acid; Activated carbon supported trifluorophosphonium bisulfate phosphonic acid; Activated carbon supported pyrrolidium formate phosphonic acid; Activated carbon supported imidazolium formate phosphonic acid; Activated carbon supported pyrazolium formate phosphonic acid; Activated carbon supported oxazolium formate phosphonic acid; Activated carbon supported thiazolium formate phosphonic acid; Activated carbon supported pyridinium formate phosphonic acid; Activated carbon supported pyrimidinium formate phosphonic acid; Activated carbon supported pyrazinium formate phosphonic acid; Activated carbon supported pyrazidimium formate phosphonic acid; Activated carbon supported thiazinium formate phosphonic acid; Activated carbon supported morpholinium formate phosphonic acid; Activated carbon supported piperidinium formate phosphonic acid; Activated carbon supported piperidinium formate phosphonic acid; Activated carbon supported pyrrolidinium formate phosphonic acid; Activated carbon supported triphenylphosphonium formate phosphonic acid; Activated carbon supported trimethylphosphonium formate phosphonic acid; Activated carbon supported triethylphosphonium formate phosphonic acid; Activated carbon-supported tripropylphosphonium formate phosphonic acid; Activated carbon-supported tributylphosphonium formate phosphonic acid; Activated carbon-supported trifluorophosphonium formate phosphonic acid; Activated carbon-supported pyrrolidinium acetate phosphonic acid; Activated carbon-supported imidazolium acetate phosphonic acid; Activated carbon-supported pyrazolium acetate phosphonic acid; Activated carbon-supported oxazolium acetate phosphonic acid; Activated carbon-supported thiazolium acetate phosphonic acid; Activated carbon-supported pyridinium acetate phosphonic acid; Activated carbon-supported pyrimidinium acetate phosphonic acid; Activated carbon-supported pyrazinium acetate phosphonic acid; Activated carbon-supported pyrazidimium acetate phosphonic acid; Activated carbon-supported thiazinium acetate phosphonic acid; Activated carbon-supported morpholinium acetate phosphonic acid; Activated carbon-supported piperidinium acetate phosphonic acid; Activated carbon-supported piperidinium acetate phosphonic acid; Activated carbon-supported pyrrolidinium acetate phosphonic acid; Activated carbon-supported triphenylphosphonium acetate phosphonic acid; Activated carbon-supported trimethylphosphonium acetate phosphonic acid; Activated carbon-supported triethylphosphonium acetate phosphonic acid; Activated carbon-supported tripropylphosphonium acetate phosphonic acid; Activated carbon-supported tributylphosphonium acetate phosphonic acid; Activated carbon-supported trifluorophosphonium acetate phosphonic acid; Activated carbon-supported ethanoyl-triphosphonium sulfonic acid; Activated carbon-supported ethanoyl-methylmorpholinium sulfonic acid; and Activated carbon-supported ethanoyl-imidazolium sulfonic acid selected from.

[0246] The methods for preparing the polymer catalysts and solid-supported catalysts described herein can be found in WO2014 / 031956, which is hereby incorporated herein by reference, specifically with respect to paragraphs

[0345] to

[0380] and

[0382] to

[0472] .

[0247] Reaction conditions for oligosaccharide formation by the catalyst In some embodiments, the feedstock sugar and the catalyst (e.g., a polymer catalyst or a solid-supported catalyst) are reacted for at least 5 minutes, at least 10 minutes, at least 15 minutes, at least 30 minutes, at least 45 minutes, at least 1 hour, at least 2 hours, at least 3 hours, at least 4 hours, at least 6 hours, at least 8 hours, at least 16 hours, at least 24 hours, at least 36 hours or at least 48 hours, or for 15 - 60 minutes, 30 - 60 minutes, 45 - 60 minutes, 1 - 24 hours, 2 - 12 hours, 3 - 6 hours, 1 - 96 hours, 12 - 72 hours, or 12 - 48 hours.

[0248] In some embodiments, the degree of polymerization of one or more oligosaccharides produced according to the methods described herein can be adjusted by the reaction time. For example, in some embodiments, the degree of polymerization of one or more oligosaccharides increases by increasing the reaction time, while in other embodiments, the degree of polymerization of one or more oligosaccharides decreases by shortening the reaction time.

[0249] Reaction pressure The reaction pressure in the methods described herein can affect the reaction rate. In some embodiments, the reaction pressure is maintained in the range of about 0.05 bar to about 5.0 bar. In certain embodiments, the pressure is about 0.3 bar to about 1.0 bar, about 0.3 to about 0.9 bar, about 0.4 to about 0.7 bar, or about 0.4 to about 0.6 bar.

[0250] Reaction temperature The reaction temperature in the method described herein can affect the reaction rate and yield. In some embodiments, the reaction temperature is maintained in the range of about 25°C to about 180°C. In certain embodiments, the temperature is about 60°C to about 160°C, about 90°C to about 150°C, about 100°C to about 150°C, about 110°C to about 1500°C, about 95°C to about 105°C, or about 140°C to 150°C.

[0251] Amount of feedstock sugar In the method described herein, the amount of feedstock sugar relative to the amount of solvent used can affect the reaction rate and yield. The amount of feedstock sugar used can be characterized by the dry solid content. In certain embodiments, the dry solid content refers to the total of the solids of the slurry as a percentage (percent) on a dry weight basis. In some embodiments, the dry solid content of the feedstock sugar is about 5 wt% to about 95 wt%, about 10 wt% to about 80 wt%, about 15 to about 75 wt%, or about 15 to about 50 wt%.

[0252] Amount of catalyst The amount of catalyst used in the method described herein can depend on several factors including, for example, the choice of the type of feedstock sugar, the concentration of the feedstock sugar, and the reaction conditions (e.g., temperature, time, and pressure). In some embodiments, the weight ratio of the catalyst to the feedstock sugar is about 0.01 g / g to about 50 g / g, about 0.01 g / g to about 5 g / g, about 0.05 g / g to about 1.0 g / g, about 0.05 g / g to about 0.5 g / g, about 0.05 g / g to about 0.2 g / g, or about 0.1 g / g to about 0.2 g / g.

[0253] Solvent In certain embodiments, the method using the catalyst is carried out in an aqueous environment. One suitable aqueous solvent is water, which can be obtained from various sources. Generally, a water source with a lower concentration of ionic species (e.g., salts of sodium, phosphorus, ammonium, or magnesium) is preferred, as such ionic species can reduce the effectiveness of the catalyst. In some embodiments where the aqueous solvent is water, the water has a resistivity of at least 0.1 megaohm - centimeter, at least 1 megaohm - centimeter, at least 2 megaohm - centimeter, at least 5 megaohm - centimeter, or at least 10 megaohm - centimeter.

[0254] Moisture content Furthermore, as the dehydration reaction of the method proceeds, water is produced for each coupling of one or more sugars. In certain embodiments, the methods described herein can further include the step of monitoring, over time, the amount of water present in the reaction mixture and / or the ratio of water to sugar or catalyst. In some embodiments, the method further includes removing at least a portion of the water produced in the reaction mixture (e.g., by vacuum evaporation, etc., removing at least any one of about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, about 97%, about 99%, or about 100%). However, it is understood that the amount of water relative to the sugar can be adjusted based on the reaction conditions used and the particular catalyst.

[0255] The water in the reaction mixture can be removed using any method known in the art, including, for example, membrane filtration, vacuum distillation, heating, and / or evaporation. In some embodiments, the method includes the step of including water in the reaction mixture.

[0256] In one aspect, provided herein is a method for producing an oligosaccharide composition by forming a reaction mixture of a feedstock sugar and a catalyst having an acidic site and an ionic site, generating water in the reaction mixture, and removing at least a portion of the water generated in the reaction mixture. In certain variations, at least a portion of the water is removed to maintain a water content of less than 99 wt%, less than 90 wt%, less than 80 wt%, less than 70 wt%, less than 60 wt%, less than 50 wt%, less than 40 wt%, less than 30 wt%, less than 20 wt%, less than 10 wt%, less than 5 wt%, or less than 1 wt% in the reaction mixture.

[0257] In some embodiments, the degree of polymerization of the oligosaccharide composition or functionalized oligosaccharide composition produced according to the methods described herein can be adjusted by regulating or controlling the concentration of water present in the reaction mixture. For example, in some embodiments, the degree of polymerization of the oligosaccharide composition increases by decreasing the concentration of water, while in other embodiments, the degree of polymerization of the oligosaccharide composition decreases by increasing the concentration of water. In some embodiments, the water content of the reactants is adjusted during the reaction to adjust the degree of polymerization of the resulting oligosaccharide composition.

[0258] Batch process vs. continuous process Generally, the catalyst and the feedstock sugar are introduced into the internal chamber of the reactor either simultaneously or sequentially. The reaction can be carried out in a batch process or a continuous process. For example, in one embodiment, the method is carried out in a batch process in which the contents of the reactor are continuously mixed or blended and all or most of the amount of the reaction product is withdrawn. In one variation, the method is carried out in a batch process in which the contents of the reactor are first combined or mixed, but no further physical mixing is performed. In another variation, the method is carried out in a batch process in which further mixing of the contents, or periodic mixing of the contents of the reactor, is once performed (e.g., more than once per hour), and all or most of the amount of the reaction product is withdrawn after a certain period.

[0259] In some embodiments, the method is repeated in a continuous batch process in which at least a portion of the catalyst is separated from at least a portion of the oligosaccharide composition produced (e.g., as described in more detail below) and reused by further contacting with additional feedstock sugar.

[0260] For example, in one aspect, a) combining a feedstock sugar and a catalyst to form a reaction mixture, wherein the catalyst comprises an acidic monomer and an ionic monomer linked to form a polymer backbone, or the catalyst comprises a solid support, an acidic site bonded to the solid support, and an ionic site bonded to the solid support; b) producing an oligosaccharide composition from at least a portion of the reaction mixture; c) separating the oligosaccharide composition from the catalyst; d) combining additional feedstock sugar and the separated catalyst to form a further reaction mixture; and e) producing a further oligosaccharide composition from at least a portion of the further reaction mixture. A method for producing an oligosaccharide composition is provided.

[0261] In some embodiments where the method is carried out in a batch process, the catalyst is reused at least 1, at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, or at least 10 times (e.g., steps (c)-(e) above are repeated). In some of these embodiments, the catalyst retains at least 80% activity (e.g., at least 90%, 95%, 96%, 97%, 98%, or 99% activity) after 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 reuses when comparing the catalytic activity under the same conditions as before reuse.

[0262] In other embodiments, the method is carried out in a continuous process in which the contents flow through the reactor at an average continuous flow rate. After introducing the catalyst and the feedstock sugar into the reactor, the contents of the reactor are mixed or blended continuously or periodically, and after a while, less than all of the reaction product is withdrawn. In one variation, the method is carried out in a horizontal thin-film reactor. In another variation, the method is carried out in a horizontal or vertical reactor that includes a static mixer. In yet another variation, the method is carried out in a continuous process in which the mixture containing the catalyst and one or more sugars is not actively mixed. Further, the mixing of the catalyst and the feedstock sugar can occur as a result of redistribution of catalyst sedimentation by gravity or as a result of non-active mixing that occurs as the feedstock flows through the continuous reactor. In some embodiments of the method, the step of combining the feedstock sugar and the catalyst and the step of isolating the resulting oligosaccharide composition are carried out simultaneously.

[0263] reactor The reactor used in the method described in this specification can be an open or closed reactor suitable for containing and using the chemical reactants described in this specification. Suitable reactors can include, for example, a fed-batch stirred reactor, a batch stirred reactor, a continuous flow stirred reactor with ultrafiltration, a horizontal thin film reactor, a vertical thin film reactor, a continuous plug flow column reactor, an attrition reactor, or a reactor equipped with a powerful stirrer induced by an electromagnetic field.For example, see Fernanda de Castilhos Corazza, Flavio Faria de Moraes, Gisella Maria Zanin and Ivo Neitzel, Optimal control in fed-batch reactor for the cellobiose hydrolysis, Acta Scientiarum. Technology, Vol. 25: pp. 33-38 (2003), Gusakov, A. V. and Sinitsyn, A. P., Kinetics of the enzymatic hydrolysis of cellulose: 1. A mathematical model for a batch reactor process, Enz. Microb. Technol., Vol. 7: pp. 346-352 (1985), Ryu, S. K. and Lee, J. M., Bioconversion of waste cellulose by using an attrition bioreactor, Biotechnol. Bioeng. 25: pp. 53-65 (1983), Gusakov, A. V., Sinitsyn, A. P., Davydkin, I. Y., Davydkin, V. Y., Protas, O. V., Enhancement of enzymatic cellulose hydrolysis using a novel type of bioreactor with intensive stirring induced by electromagnetic field, Appl. Biochem. Biotechnol., Vol. 56: pp. 141-153 (1996). Other suitable types of reactors can include, for example, fluidized bed, upflow blanket, fixed, and extruder type reactors for hydrolysis and / or fermentation.

[0264] In certain embodiments, where the method is carried out as a continuous process, the reactor may include a continuous mixer such as a screw mixer. The reactor can generally be made of materials capable of withstanding the physical and chemical forces exerted during the methods described herein. In some embodiments, such materials used in the reactor can withstand high concentrations of strong acid liquids, while in other embodiments, such materials may not exhibit resistance to strong acids.

[0265] It is further understood that additional feed sugars and / or catalysts may be added to the reactor either simultaneously or sequentially.

[0266] Separation and purification In some embodiments, the methods described herein further include the step of isolating one or more oligosaccharides produced. In some embodiments, the methods described herein further include the step of isolating one or more functionalized oligosaccharides produced. In some of these embodiments, the step of isolating one or more oligosaccharides and / or functionalized oligosaccharides includes separating at least a portion of the one or more oligosaccharides from at least a portion of the polymer catalyst (e.g., by suction filtration, pressure filtration, centrifugation, sedimentation, or cyclone separation). In some of these embodiments, the step of isolating one or more oligosaccharides further includes separating at least a portion of the one or more oligosaccharides from at least a portion of any unreacted sugars (e.g., by chromatography). In other embodiments, the step of isolating one or more functionalized oligosaccharides further includes separating at least a portion of the one or more functionalized oligosaccharides from at least a portion of any unreacted sugars and / or unreacted functionalized compounds (e.g., by chromatography).

[0267] One or more oligosaccharides or functionalized oligosaccharides can be separated from insoluble substances in the reaction mixture, such as solid polymer catalysts, using techniques well known in the art, such as centrifugation, filtration (e.g., suction filtration or pressure filtration), and gravitational sedimentation. One or more oligosaccharides or functionalized oligosaccharides can be separated from one or more sugars in the reaction mixture or one or more functionalized compounds in the reaction mixture using techniques well known in the art, including but not limited to chromatography, electrophoresis procedures, solubility differences, or extraction.

[0268] The oligosaccharides isolated from the vessel can be subjected to further processing steps (e.g., drying) or subsequent chemical treatment.

[0269] In some embodiments, the one or more oligosaccharides to be isolated are substantially pure. With respect to a method, "substantially pure" is intended to mean an isolated preparation of one or more oligosaccharides that contains 25% (w / w) or less of non-oligosaccharide substances as determined by analytical procedures known in the art, such as high performance liquid chromatography (HPLC), nuclear magnetic resonance (NMR) spectroscopy, functionalization and analysis by gas chromatography, mass spectrometry, spectroscopic procedures based on chromophore complex formation, and / or measurement by carbohydrate oxidation-reduction chemistry. In some embodiments, a substantially pure preparation contains 20% or less, or 15% or less, or 10% or less, or 7.5% or less, or 5% or less, or 3% or less, or 2% or less, or 1% or less, or 0.5% or less, or 0.1% or less of non-oligosaccharide substances.

[0270] Reusability of the catalyst In the method for producing an oligosaccharide composition comprising a functionalized oligosaccharide composition described herein, the catalyst containing acidic groups and ionic groups can be reused. Thus, in one aspect, a method for producing an oligosaccharide composition using a reusable catalyst is provided herein. These methods include combining one or more sugars with a catalyst to produce a product mixture, wherein the product mixture comprises an oligosaccharide composition and a residual catalyst, isolating at least a portion of the residual catalyst from the product mixture, and combining one or more additional sugars with the isolated residual catalyst to produce a further product mixture.

[0271] It is understood that during use and / or reuse, a portion of the catalyst may undergo chemical decomposition (e.g., oxidation, de-functionalization, depolymerization, or contamination) and / or physical decomposition (e.g., in the case of a solid-supported catalyst, cracking of the support). Thus, in some embodiments, at least a portion of the residual catalyst is chemically and / or physically different from the initial (first) catalyst combined with the sugar in the first step. In some embodiments, sugars or reaction by-products may adsorb reversibly or irreversibly onto the catalyst.

[0272] In some embodiments of the above-described reuse method, one or more sugars and the catalyst are further combined with one or more functionalized compounds to produce a functionalized oligosaccharide composition. In other embodiments of the above-described method, the oligosaccharide composition is combined with one or more functionalized compounds and the isolated residual catalyst to produce a functionalized oligosaccharide composition.

[0273] For example, any method known in the art including centrifugation, filtration (e.g., pressure filtration, suction filtration), phase separation, and gravitational sedimentation can be used to separate the catalyst for reuse.

[0274] The methods described herein can be carried out as batch processes or continuous processes. Reuse in a batch process can include, for example, the step of recovering the catalyst from the reaction mixture and the step of reusing the recovered catalyst in one or more subsequent reaction cycles. Reuse in a continuous process can include, for example, the step of introducing additional feed sugar into the reactor without adding fresh catalyst.

[0275] In some embodiments where at least a portion of the catalyst is reused, the catalyst is reused at least once, at least twice, at least three times, at least four times, at least five times, at least six times, at least seven times, at least eight times, at least nine times, or at least ten times. In some of these embodiments, when comparing the catalytic activity of the catalyst under the same conditions as before reuse, after being reused one, two, three, four, five, six, seven, eight, nine, or ten times, it retains at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% of its activity. In some variations, the catalytic activity of the isolated catalyst in the production of a further oligosaccharide composition is at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% of the catalytic activity of the catalyst in the production of the first oligosaccharide composition. In some variations, the catalytic activity of the residual catalyst in the production of a further oligosaccharide composition is at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% of the catalytic activity of the catalyst in the production of the first oligosaccharide composition.

[0276] As used herein, "catalytic activity" refers to the effective first-order rate constant with respect to the molar conversion of the reactant, k = -ln(1 - X(t)) / t. The molar conversion of reactant A at time t is defined as X A (t) = 1 - mol(A,t) / mol(A,0), where mol(A,t) refers to the number of moles of species A present in the reaction mixture at time t, and mol(A,0) refers to the number of moles of species A present at the start of the reaction, t = 0. In practice, the number of moles of reactant A is measured at several points at times t 1 , t 2 , t 3 , ···, t n and is often used to calculate the conversion rates X A (t 1 ), X A (t 2 ), ··· X A (t n ) at the corresponding times. Next, the first-order rate constant k is calculated by fitting the data for X A (t).

[0277] As used herein, a reaction "cycle" refers to one period of use within a series of uses of a catalyst. For example, in a batch process, a reaction cycle corresponds to an individual step among the steps of charging the reactant and the catalyst into the reactor system, heating the reactants under conditions suitable for converting the reactant, maintaining a specific residence time and reaction conditions, separating the reaction product from the catalyst, and recovering the catalyst for reuse. In a continuous process, one cycle refers to the space time of a single reactor during the operation of the continuous process. For example, in a 1,000-liter reactor with a continuous volume flow rate of 200 liters per hour, the space time of the continuous reactor is 2 hours, the first 2 hours of continuous operation is the first reaction cycle, the next 2 hours of continuous operation is the second reaction cycle, and so on. Therefore, the catalyst reuse method described herein includes a continuous process in which the catalyst is used over multiple reaction cycles to produce a reaction mixture containing an oligosaccharide composition.

[0278] As used herein, "loss of activity" or "activity loss" of a catalyst is determined by the average rate of decrease in catalyst activity between consecutive cycles. For example, if the catalyst activity in reaction cycle 1 is k(1) and the catalyst activity in reaction cycle 2 is k(2), the loss of catalyst activity between cycle 1 and cycle 2 is calculated as [k(2) - k(1)] / k(1). Next, the loss of activity over N reaction cycles is measured in units of loss rate per cycle,

[0279]

Number

[0280] In some variations, the rate constant for the conversion of the additional feedstock sugar is less than 20% lower than the rate constant for the conversion of the feedstock sugar that is the reactant in the first reaction. In certain variations, the rate constant for the conversion of the additional feedstock sugar is less than 15%, less than 12%, less than 10%, less than 8%, less than 6%, less than 4%, less than 2%, or less than 1% lower than the rate constant for the conversion of the feedstock sugar that is the reactant in the first reaction. In some variations, the loss of activity is less than 20% per cycle, less than 15% per cycle, less than 10% per cycle, less than 8% per cycle, less than 4% per cycle, less than 2% per cycle, less than 1% per cycle, less than 0.5% per cycle, or less than 0.2% per cycle.

[0281] In other variations, the rate constant for the conversion of the further functionalized compound is less than 20% lower than the rate constant for the conversion of the functionalized compound in the first reaction. In certain variations, the rate constant for the conversion of the further functionalized compound is less than 15%, less than 12%, less than 10%, less than 8%, less than 6%, less than 4%, less than 2%, or less than 1% lower than the rate constant for the conversion of the functionalized compound in the first reaction. In some variations, the loss of activity is less than 20% per cycle, less than 15% per cycle, less than 10% per cycle, less than 8% per cycle, less than 4% per cycle, less than 2% per cycle, less than 1% per cycle, less than 0.5% per cycle, or less than 0.2% per cycle.

[0282] As used herein, "catalyst life" refers to the average number of cycles that catalyst particles can be reused until the catalyst particles no longer effectively catalyze the conversion of the feedstock sugar, which is the further reactant. Catalyst life is calculated as the reciprocal of the loss of activity. For example, if the loss of activity is 1% per cycle, the catalyst life is 100 cycles. In some variations, the catalyst life is at least 1 cycle, at least 2 cycles, at least 10 cycles, at least 50 cycles, at least 100 cycles, at least 200 cycles, or at least 500 cycles.

[0283] In certain embodiments, a portion of the total mass of the catalyst during the reaction can be removed between reaction cycles and replaced with fresh catalyst. For example, in some variations, 0.1% of the mass of the catalyst can be replaced between reaction cycles, 1% of the mass of the catalyst can be replaced between reaction cycles, 2% of the mass of the catalyst can be replaced between reaction cycles, 5% of the mass of the catalyst can be replaced between reaction cycles, 10% of the mass of the catalyst can be replaced between reaction cycles, or 20% of the mass of the catalyst can be replaced between reaction cycles.

[0284] As used herein, "catalyst composition ratio" refers to the fraction of the catalyst mass that is replaced with fresh catalyst between reaction cycles.

[0285] Refactoring of Bonds The sugars used in the methods described herein typically have α-1,4 linkages and, when used as reactants in the methods described herein, at least a portion of the α-1,4 linkages are converted to β-1,4, α-1,3, β-1,3, α-1,6, and β-1,6 linkages.

[0286] Thus, in certain embodiments, combining a feedstock sugar and a catalyst to form a reaction mixture, wherein the feedstock sugar comprises α-1,4 linkages, the catalyst comprises acidic monomers and ionic monomers linked to form a polymer backbone, or the catalyst comprises a solid support, acidic sites bonded to the solid support, and ionic sites bonded to the solid support, and converting at least a portion of the α-1,4 linkages in the feedstock sugar to one or more non-α-1,4 linkages selected from the group consisting of β-1,4, α-1,3, β-1,3, α-1,6, and β-1,6 linkages to produce an oligosaccharide composition from at least a portion of the reaction mixture A method for producing an oligosaccharide composition is provided.

[0287] It is generally understood that α-1,4 linkages are also referred to herein as α(1,4) linkages and, similarly, β-1,4, α-1,3, β-1,3, α-1,6, and β-1,6 linkages can each also be referred to as β(1,4), α(1,3), β(1,3), α(1,6), and β(1,6) linkages.

[0288] In another variation, a method is described herein for converting a polysaccharide having mainly one type of glycosidic bond into a polysaccharide having a mixture of various glycosidic bonds. In one embodiment, the polysaccharide used in the method described herein typically has α-1,4 linkages, and when used as a reactant in the method described herein, at least a portion of the α-1,4 linkages are converted to β-1,4 linkages, α-1,3 linkages, β-1,3 linkages, α-1,6 linkages, and β-1,6 linkages.

[0289] Thus, in certain aspects, contacting an α-1,4 polysaccharide with a catalyst, wherein the catalyst comprises an acidic monomer and an ionic monomer linked to form a polymer backbone, or the catalyst comprises a solid support, an acidic site bonded to the solid support, and an ionic site bonded to the solid support, and converting at least a portion of the α-1,4 linkages in the α-1,4 polysaccharide to one or more non-α-1,4 linkages selected from the group consisting of α-1,2 linkages, β-1,2 linkages, α-1,3 linkages, β-1,3 linkages, β-1,4 linkages, α-1,6 linkages, and β-1,6 linkages to produce a polysaccharide having a mixed linking group from at least a portion of the α1,4 polysaccharide, thereby providing a method for converting an α-1,4 polysaccharide to a polysaccharide having a mixed linking group. In some variations, the one or more non-α-1,4 linkages are selected from the group consisting of β-1,4 linkages, α-1,3 linkages, β-1,3 linkages, α-1,6 linkages, and β-1,6 linkages.

[0290] In some embodiments, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% of the α-1,4 polysaccharide contains α-1,4 linkages. In some variations, the α-1,4 polysaccharide comprises starch. In certain variations, the α-1,4 polysaccharide is starch.

[0291] In some embodiments, the polysaccharide having a mixed linking group contains at least two, at least three, at least four, at least five, or at least six or more types of non-α-1,4 glycosidic linkages. In some variations, the types of non-α-1,4 glucosidic linkages are selected from the group consisting of α-1,2 linkages, β-1,2 linkages, α-1,3 linkages, β-1,3 linkages, β-1,4 linkages, α-1,6 linkages, and β-1,6 linkages.

[0292] In other embodiments, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 99% of the generated polysaccharide contains a mixed non-α-1,4 linkage.

[0293] It is generally understood that α-1,4 linkages are also referred to herein as α(1,4) linkages, and similarly, β-1,4 linkages, α-1,3 linkages, β-1,3 linkages, α-1,6 linkages, and β-1,6 linkages can be referred to as β(1,4), α(1,3), β(1,3), α(1,6), and β(1,6) linkages, respectively.

[0294] Oligosaccharide composition Also provided herein are oligosaccharides (including functionalized oligosaccharides) and oligosaccharide compositions (including functionalized oligosaccharide compositions) obtained by any of the methods described herein.

[0295] The oligosaccharides generated from the methods described herein depend on both the selection of one or more sugars and the reaction conditions used. The oligosaccharide content of the reaction product can be determined, for example, by combining high performance liquid chromatography (HPLC) and spectrophotometry as described in the items of the following examples. For example, the average degree of polymerization (DP) for oligosaccharides can be determined as the number average of species containing 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 to 15, and more than 15 monomer units of anhydro sugars.

[0296] In some embodiments, after combining one or more sugars and a polymer catalyst (e.g., after combining one or more sugars and a polymer catalyst, 2 hours later, 3 hours later, 4 hours later, 8 hours later, 12 hours later, 24 hours later, or 48 hours later), the degree of polymerization (DP) distribution of the oligosaccharides with respect to one or more oligosaccharides is such that DP2 = 0% to 40% (e.g., less than 40%, less than 30%, less than 20%, less than 10%, less than 5%, or less than 2%), or 10% to 30% or 15% to 25%, DP3 = 0% to 20% (e.g., less than 15%, less than 10%, less than 5%), or 5% to 15%, and DP4+ > 15%, > 20%, > 30%, > 40%, > 50%, or 15% to 75%, 20% to 40% or 25% to 35%.

[0297] In some embodiments, after combining one or more sugars, an oligosaccharide composition, or a combination thereof with a functionalized compound and a polymer catalyst (e.g., after combining with the polymer catalyst, 2 hours later, 3 hours later, 4 hours later, 8 hours later, 12 hours later, 24 hours later, or 48 hours later), the degree of polymerization (DP) distribution of the oligosaccharides with respect to the functionalized oligosaccharide composition is such that DP2 = 0% to 40% (e.g., less than 40%, less than 30%, less than 20%, less than 10%, less than 5%, or less than 2%), or 10% to 30% or 15% to 25%, DP3 = 0% to 20% (e.g., less than 15%, less than 10%, less than 5%), or 5% to 15%, and DP4+ > 15%, > 20%, > 30%, > 40%, > 50%, or 15% to 75%, 20% to 40% or 25% to 35%.

[0298] In some embodiments, after combining one or more sugars and a catalyst (e.g., after combining one or more sugars and a catalyst, 2 hours later, 3 hours later, 4 hours later, 8 hours later, 12 hours later, 24 hours later, or 48 hours later), the degree of polymerization (DP) distribution of the oligosaccharides with respect to one or more oligosaccharides is any one of entries (1) to (192) in Table 1A.

[0299] [Table 1] TIFF2025084883000035.tif24180TIFF2025084883000036.tif24180TIFF2025084883000037.tif24180TIFF2025084883000038.tif14981

[0300] In some embodiments, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99%, or at least 100% of the oligosaccharide composition, comprising a functionalized oligosaccharide composition generated by the methods described herein, has a number average molecular weight of 230 - 10,000 g / mol, 420 - 9,000 g / mol, 500 - 8,000 g / mol. In one embodiment, at least 10% of the oligosaccharide composition has a number average molecular weight of 500 - 8,000 g / mol.

[0301] The conversion yield of one or more sugars to one or more oligosaccharides, including the functionalized oligosaccharide, in the methods described herein can be determined as described, for example, in the items of the following examples. In some embodiments, after combining one or more sugars and the polymer catalyst (e.g., after combining one or more sugars and the polymer catalyst, after 2 hours, 3 hours, 4 hours, 8 hours, 12 hours, 24 hours, or 48 hours), the conversion yield to one or more oligosaccharides having DP>1 is greater than about 50% (e.g., greater than about 55%, greater than about 60%, greater than about 65%, greater than about 70%, greater than about 75%, greater than about 80%, greater than about 85%, greater than about 90%, greater than about 95%, or greater than about 98%). In some embodiments, after combining one or more sugars and the polymer catalyst (e.g., after combining one or more sugars and the polymer catalyst, after 2 hours, 3 hours, 4 hours, 8 hours, 12 hours, 24 hours, or 48 hours), the conversion yield to one or more oligosaccharides having >DP2 is greater than 30% (e.g., greater than 35%, greater than 40%, greater than 45%, greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90%, greater than 95%, or greater than 98%).

[0302] As shown in the following examples, the methods described herein result in significantly lower levels of decomposition products and relatively high selectivity when compared to existing catalysts. The molar yields and selectivities to sugar decomposition products can be determined, for example, as described in the items of the following examples. In some embodiments, after combining one or more sugars and one or more functionalized compounds (where applicable) with the polymeric catalyst (e.g., after combining one or more sugars with the polymeric catalyst, after 2 hours, 3 hours, 4 hours, 8 hours, 12 hours, 24 hours, or 48 hours), the amount of sugar decomposition products is less than about 24% (e.g., less than about 23%, less than about 22%, less than about 21%, less than about 20%, less than about 19%, less than about 18%, less than about 17%, less than about 16%, less than about 15%, less than about 14%, less than about 13%, less than about 12%, less than about 11%, less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, less than about 1%, less than about 0.75%, less than about 0.5%, less than about 0.25%, or less than about 0.1%), for example, less than about 24% of any one or combination of 1,6-anhydroglucose (levoglucosan), 5-hydroxymethylfurfural, 2-furaldehyde, acetic acid, formic acid, levulinic acid, and / or humin. In some embodiments, after combining one or more sugars and one or more functional compounds (where applicable) with the polymeric catalyst (e.g., after combining one or more sugars with the polymeric catalyst, after 2 hours, 3 hours, 4 hours, 8 hours, 12 hours, 24 hours, or 48 hours), the molar selectivity to oligosaccharide (including functionalized oligosaccharide) products is greater than about 86% (e.g., greater than about 87%, greater than about 88%, greater than about 89%, greater than about 90%, greater than about 91%, greater than about 92%, greater than about 93%, greater than about 94%, greater than about 95%, greater than about 97%, greater than about 98%, greater than about 99%, greater than about 99.5%, or greater than about 99.9%). In one embodiment, the molar selectivity to oligosaccharides, including functionalized oligosaccharides, after combining one or more sugars and one or more functional compounds (where applicable) with the polymeric catalyst is greater than about 86%.

[0303] Digestibility In some variations, "digestibility" refers to the ability of the human or animal stomach and / or small intestine to digest (e.g., hydrolyze) a compound. Compounds that are resistant to digestion include, for example, dietary fiber. The digestibility of one or more oligosaccharides produced by the methods described herein can be determined by standard methods known to those skilled in the art, such as, for example, the AOAC 2009.01, an in vitro method, or the in vitro Englyst Assay. AOAC 2009.01 is an enzyme assay that can determine the amount of a carbohydrate composition that is dietary fiber. See Official Methods of Analysis of AOAC International, AOAC International, Gaithersberg, USA. The Englyst Assay is an enzyme assay that can determine the amount of a carbohydrate composition that is rapidly digestible, slowly digestible, or resistant to digestion. See European Journal of Clinical Nutrition (1992) 46, Suppl. 2, pp. S33 - S60.

[0304] In some embodiments, more than 50% (e.g., more than 55%, more than 60%, more than 70%, more than 80%, more than 90%, more than 99%) of one or more oligosaccharides produced by the methods described herein are dietary fiber. In some embodiments, less than 50%, less than 40%, less than 30%, less than 20%, less than 10%, less than 5%, or less than 1% of an oligosaccharide composition having 3 or more DPs is hydrolyzed to an oligosaccharide having 2 DPs and / or a monosaccharide.

[0305] Glass transition temperature In some variations, "glass transition" refers to the reversible transition of a compound from a hard and relatively brittle state to a soft, flexible state. In some variations, "glass transition temperature" refers to the temperature determined by differential scanning calorimetry.

[0306] The glass transition temperature of a substance can impart desired characteristics to that substance and / or to a composition containing that substance. In some embodiments, one or more oligosaccharides having a specific glass transition temperature or within a glass transition temperature range are produced using the methods described herein. In some variations, the glass transition temperature of one or more oligosaccharides (including functionalized oligosaccharides) produced by the methods described herein imparts desired characteristics (e.g., texture, storage, or processability characteristics) to the one or more oligosaccharides. In certain variations, the glass transition temperature of one or more oligosaccharides imparts desired characteristics (e.g., texture, storage, or processability characteristics) to a composition containing the one or more oligosaccharides.

[0307] In some embodiments, the glass transition temperature of one or more oligosaccharides or functionalized oligosaccharides is at least 0 degrees Celsius, at least 10 degrees Celsius, at least 20 degrees Celsius, at least 30 degrees Celsius, at least 40 degrees Celsius, at least 50 degrees Celsius, at least 60 degrees Celsius, at least 70 degrees Celsius, at least 80 degrees Celsius, at least 90 degrees Celsius, or at least 100 degrees Celsius when prepared in dry powder form having a moisture content of less than 6%. In certain embodiments, the glass transition temperature of one or more oligosaccharides or functionalized oligosaccharides is between 40 degrees Celsius and 80 degrees Celsius.

[0308] Hygroscopicity In some variations, "hygroscopicity" refers to the ability of a compound to attract and retain water molecules from the surrounding environment. The hygroscopicity of a substance can impart desired characteristics to that substance and / or to a composition containing that substance. In some embodiments, one or more oligosaccharides having a specific hygroscopicity value or range of hygroscopicity values are produced using the methods described herein. In some variations, the hygroscopicity of one or more oligosaccharides produced by the methods described herein imparts desired characteristics (e.g., texture, storage, or processability characteristics) to the one or more oligosaccharides. In certain variations, the hygroscopicity of one or more oligosaccharides (including functionalized oligosaccharides) imparts desired characteristics (e.g., texture, storage, or processability characteristics) to a composition containing the one or more oligosaccharides.

[0309] The hygroscopicity of a composition containing one or more oligosaccharides can be determined by measuring the mass increase of the composition after equilibrium in a constant water activity atmosphere (e.g., a desiccator maintained at a constant relative humidity).

[0310] In some embodiments, the hygroscopicity of one or more oligosaccharides is at least 5% water content at a water activity of at least 0.6, at least 10% water content at a water activity of at least 0.6, at least 15% water content at a water activity of at least 0.6, at least 20% water content at a water activity of at least 0.6, or at least 30% water content at a water activity of at least 0.6. In certain embodiments, the hygroscopicity of one or more oligosaccharides is from 5% water content to 15% water content at a water activity of at least 0.6.

[0311] Fiber content In some variations, "dietary fiber" is a carbohydrate (i.e., oligosaccharide or polysaccharide) having a degree of polymerization of at least 3, which in humans or animals is not effectively hydrolyzed to its constituent sugars by enzymes (e.g., α - amylase, amyloglucosidase, and protease) in the stomach or small intestine. In some embodiments, the dietary fiber is insoluble in water. In other embodiments, the dietary fiber is soluble in water. In certain embodiments, the dietary fiber is soluble in water up to a maximum concentration of at least 10 Brix, at least 20 Brix, at least 30 Brix, at least 40 Brix, at least 50 Brix, at least 60 Brix, at least 70 Brix, at least 80 Brix, or at least 80 Brix. In one embodiment, the dietary fiber is soluble at a maximum concentration of 75 - 90 Brix.

[0312] For example, the dietary fiber content of a composition comprising the dietary fiber content of one or more oligosaccharides described herein is determined by the in vitro method AOAC 2009.01 (Official Methods of Analysis of AOAC International, AOAC International, Gaithersberg, USA), and the fraction of oligosaccharides in the composition having a degree of polymerization (DP) of at least 3 and not hydrolyzed by the combination of enzymes: α - amylase, amyloglucosidase, and protease can be quantified.

[0313] In some embodiments, the dietary fiber content of one or more oligosaccharides is at least 50% on a dry mass basis, at least 60% on a dry mass basis, at least 70% on a dry mass basis, at least 80% on a dry mass basis, or at least 90% on a dry mass basis. In certain embodiments, the dietary fiber content of one or more oligosaccharides is 70% - 80% on a dry mass basis.

[0314] In some embodiments, the average degree of polymerization (DP), glass transition temperature (Tg), hygroscopicity, and fiber content of an oligosaccharide composition produced by combining one or more sugars and a catalyst (e.g., by combining one or more sugars and a catalyst at 2 hours, 3 hours, 4 hours, 8 hours, 12 hours, 24 hours, or 48 hours later) is any one of entries (1)-(180) in Table 1B.

[0315] [Table 2] TIFF2025084883000040.tif240123TIFF2025084883000041.tif240122TIFF2025084883000042.tif239123TIFF2025084883000043.tif186124

[0316] In one aspect, a composition is provided that includes one or more oligosaccharides described herein and a polymeric catalyst described herein. In some embodiments, the composition further includes a solvent (e.g., water).

[0317] In yet another aspect, a composition is provided that includes a polymeric catalyst described herein, one or more oligosaccharides described herein, and one or more residual sugars described herein.

[0318] Enumeration of Embodiments The embodiments listed below are representative of some aspects of the present invention.

[0319] 1. A step of forming a reaction mixture that produces one or more oligosaccharides by combining one or more sugars and a catalyst, wherein the catalyst comprises an acidic monomer and an ionic monomer linked to form a polymer backbone, or the catalyst comprises a solid support, an acidic site bonded to the solid support, and an ionic site bonded to the solid support, the step comprising a method for producing one or more oligosaccharides.

[0320] 2. The method according to embodiment 1, wherein the catalyst comprises an acidic monomer and an ionic monomer linked to form a polymer backbone.

[0321] 3. The method according to embodiment 1 or 2, wherein each acidic monomer comprises at least one Bronsted-Lowry acid.

[0322] 4. The method according to embodiment 3, wherein each Bronsted-Lowry acid is independently selected from the group consisting of sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, boronic acid, and perfluorinated acid each time it appears.

[0323] 5. The method according to any one of embodiments 1 to 4, wherein one or more of the acidic monomers are directly linked to the polymer backbone.

[0324] 6. The method according to embodiment 3 or 4, wherein one or more of the acidic monomers comprise a linker that links the Bronsted-Lowry acid to the polymer backbone.

[0325] 7. The method according to embodiment 6, wherein each linker is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate each time it appears.

[0326] 8. The Bronsted-Lowry acid and the linker form a side chain, and each side chain is

[0327]

Chemical formula

[0328] 9. The method according to any one of embodiments 1 to 8, wherein each of the ionic monomers independently contains at least one nitrogen-containing cationic group or at least one phosphorus-containing cationic group.

[0329] 10. The method according to embodiment 9, wherein the nitrogen-containing cationic group is independently selected from the group consisting of pyrrolidium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyrazidimium, thiazinium, morpholinium, piperidinium, and pyrrolidinium each time it appears.

[0330] 11. The method according to embodiment 9, wherein the phosphorus-containing cationic group is independently selected from the group consisting of triphenylphosphonium, trimethylphosphonium, triethylphosphonium, tripropylphosphonium, tributylphosphonium, trichlorophosphonium, and trifluorophosphonium each time it appears.

[0331] 12. The method according to any one of embodiments 1 to 11, wherein one or more of the ionic monomers are directly linked to the polymer backbone.

[0332] 13. The method according to any one of embodiments 9 to 11, wherein one or more of the ionic monomers contain a linker that links a nitrogen-containing cationic group or a phosphorus-containing cationic group to the polymer backbone.

[0333] 14. The method according to embodiment 13, wherein the linker is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate each time it appears.

[0334] 15. The nitrogen-containing cationic group and the linker form a side chain, and each side chain

[0335] [Chemical] The method according to embodiment 13, independently selected from the group consisting of TIFF2025084883000046.tif182138, TIFF2025084883000047.tif191124, and TIFF2025084883000048.tif50122.

[0336] 16. The phosphorus-containing cationic group and the linker form a side chain, and each side chain

[0337] [Chemical] The method according to embodiment 13, independently selected from the group consisting of

[0338] 17. The polymer main chain is selected from the group consisting of polyethylene, polypropylene, polyvinyl alcohol, polystyrene, polyurethane, polyvinyl chloride, polyphenol-aldehyde, polytetrafluoroethylene, polybutylene terephthalate, polycaprolactam, poly(acrylonitrile-butadiene-styrene), polyalkylene ammonium, polyalkylene diammonium, polyalkylene pyrrolidium, polyalkylene imidazolium, polyalkylene pyrazolium, polyalkylene oxazolium, polyalkylene thiazolium, polyalkylene pyridinium, polyalkylene pyrimidinium, polyalkylene pyrazinium, polyalkylene pyrazidimium, polyalkylene thiazinium, polyalkylene morpholinium, polyalkylene piperidinium, polyalkylene piperidinium, polyalkylene pyrrolidinium, polyalkylene triphenylphosphonium, polyalkylene trimethylphosphonium, polyalkylene triethylphosphonium, polyalkylene tripropylphosphonium, polyalkylene tributylphosphonium, polyalkylene trichlorophosphonium, polyalkylene trifluorophosphonium, and polyalkylene diazolium, and the method according to any one of embodiments 1 to 16.

[0339] 18. The method according to any one of embodiments 1 to 18, wherein the polymer is crosslinked.

[0340] 19. The method according to any one of embodiments 1 to 18, wherein the acidic monomer and the cationic monomer are arranged alternately or randomly in blocks of monomers.

[0341] 20. The method according to embodiment 19, wherein each block has 20 or fewer monomers.

[0342] 21. The method according to any one of embodiments 1 to 20, wherein the polymer further comprises a hydrophobic monomer linked to the polymer backbone, and each hydrophobic monomer contains a hydrophobic group.

[0343] 22. The method according to embodiment 21, wherein the hydrophobic group is independently selected from the group consisting of unsubstituted or substituted alkyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, or unsubstituted or substituted heteroaryl each time it appears.

[0344] 23. The method according to embodiment 21 or 22, wherein the hydrophobic group is directly linked to the polymer backbone.

[0345] 24. The method according to any one of embodiments 1 to 23, wherein the polymer further comprises an acidic-ionic monomer linked to the polymer backbone, and each acidic-ionic monomer contains a Bronsted-Lowry acid and a cationic group.

[0346] 25. The method according to embodiment 24, wherein the cationic group is a nitrogen-containing cationic group or a phosphorus-containing cationic group.

[0347] 26. The method according to embodiment 24 or 25, wherein one or more of the acidic-ionic monomers each further comprise a linker that links the Bronsted-Lowry acid or the cationic group to the polymer backbone.

[0348] 27. The method according to embodiment 26, wherein the linker is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate each time it appears.

[0349] 28. The method according to embodiment 26, wherein the Bronsted-Lowry acid, the cationic group, and the linker form a side chain, and each side chain

[0350]

Chemical formula

[0351] 29. The method according to any one of embodiments 1 to 28, wherein the polymer has a total amount of Bronsted-Lowry acid of 0.01 to 20 mmol (for example, 0.01 to 10 mmol per gram of polymer, 0.1 to 5 mmol per gram of polymer, and 0.1 to 3.0 mmol per gram of polymer) per gram of the polymer.

[0352] 30. The method according to any one of embodiments 1 to 29, wherein at least a part of the acidic monomer contains sulfonic acid.

[0353] 31. The method according to embodiment 30, wherein the total amount of sulfonic acid in the polymer is 0.05 to 10 mmol per gram of the polymer.

[0354] 32. The method according to any one of embodiments 1 to 31, wherein at least a part of the acidic monomer contains phosphonic acid.

[0355] 33. The method according to embodiment 32, wherein the total amount of phosphonic acid in the polymer is 0.01 to 12 mmol per gram of the polymer.

[0356] 34. The method according to any one of Embodiments 1 to 33, wherein at least a part of the acidic monomer contains acetic acid.

[0357] 35. The method according to Embodiment 34, wherein the total amount of acetic acid in the polymer is 0.01 to 12 mmol per gram of the polymer.

[0358] 36. The method according to any one of Embodiments 1 to 35, wherein at least a part of the acidic monomer contains isophthalic acid.

[0359] 37. The method according to Embodiment 36, wherein the total amount of isophthalic acid in the polymer is 0.01 to 5 mmol per gram of the polymer.

[0360] 38. The method according to any one of Embodiments 1 to 37, wherein at least a part of the acidic monomer contains boric acid.

[0361] 39. The method according to Embodiment 38, wherein the total amount of boric acid in the polymer is 0.01 to 20 mmol per gram of the polymer.

[0362] 40. The method according to any one of Embodiments 1 to 39, wherein at least a part of the acidic monomer contains a perfluorinated acid.

[0363] 41. The method according to Embodiment 40, wherein the total amount of the perfluorinated acid in the polymer is 0.01 to 5 mmol per gram of the polymer.

[0364] 42. The method according to any one of Embodiments 1 to 41, wherein each of the ionic monomers further contains a counter ion for each of the nitrogen-containing cationic group or the phosphorus-containing cationic group.

[0365] 43. The method according to Embodiment 42, wherein the counter ion is independently selected from the group consisting of halide ions, nitrate ions, sulfate ions, formate ions, acetate ions, or organic sulfonate ions each time it appears.

[0366] 44. The method according to embodiment 42 or 43, wherein the polymer has a total amount of nitrogen-containing cationic groups and counterions, or a total amount of phosphorus-containing cationic groups and counterions of 0.01 to 10 mmol per gram of the polymer.

[0367] 45. The method according to any one of embodiments 42 to 44, wherein at least a part of the ionic monomer contains imidazolium.

[0368] 46. The method according to embodiment 45, wherein the total amount of imidazolium and counterions in the polymer is 0.01 to 8 mmol per gram of the polymer.

[0369] 47. The method according to any one of embodiments 42 to 46, wherein at least a part of the ionic monomer contains pyridinium.

[0370] 48. The method according to embodiment 47, wherein the total amount of pyridinium and counterions in the polymer is 0.01 to 8 mmol per gram of the polymer.

[0371] 49. The method according to any one of embodiments 42 to 48, wherein at least a part of the ionic monomer contains triphenylphosphonium.

[0372] 50. The method according to embodiment 49, wherein the total amount of triphenylphosphonium and counterions in the polymer is 0.01 to 5 mmol per gram of the polymer.

[0373] 51. The polymer is poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene]; poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium acetate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium nitrate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium acetate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium nitrate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium iodide-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium bromide-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium acetate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzimidazol-1-ium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzimidazol-1-ium sulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzimidazol-1-ium acetate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-benzimidazol-1-ium formate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium-chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium-sulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium-acetate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium-nitrate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium-chloride-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium-bromide-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium-iodide-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium-sulfate-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-pyridinium-acetate-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-ium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-ium sulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-ium acetate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-methyl-4-(4-vinylbenzyl)-morpholin-4-ium formate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-triphenyl-(4-vinylbenzyl)-phosphonium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-triphenyl-(4-vinylbenzyl)-phosphonium sulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-triphenyl-(4-vinylbenzyl)-phosphonium acetate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-methyl-1-(4-vinylbenzyl)-piperidin-1-ium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-methyl-1-(4-vinylbenzyl)-piperidin-1-ium sulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-methyl-1-(4-vinylbenzyl)-piperidin-1-ium acetate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-triethyl-(4-vinylbenzyl)-ammonium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-triethyl-(4-vinylbenzyl)-ammonium sulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-triethyl-(4-vinylbenzyl)-ammonium acetate-co-divinylbenzene]; Poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-4-boronyl-1-(4-vinylbenzyl)-pyridinium chloride-co-divinylbenzene]; Poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-1-(4-vinylphenyl)methylphosphonic acid-co-divinylbenzene]; Poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-1-(4-vinylphenyl)methylphosphonic acid-co-divinylbenzene]; Poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium acetate-co-1-(4-vinylphenyl)methylphosphonic acid-co-divinylbenzene]; Poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium nitrate-co-1-(4-vinylphenyl)methylphosphonic acid-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyl chloride-co-1-methyl-2-vinyl-pyridinium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyl chloride-co-1-methyl-2-vinyl-pyridinium sulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyl chloride-co-1-methyl-2-vinyl-pyridinium acetate-co-divinylbenzene]; Poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide-co-divinylbenzene]; Poly[styrene-co-4-vinylphenylphosphonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene]; Poly[styrene-co-4-vinylphenylphosphonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene]; Poly[styrene-co-4-vinylphenylphosphonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium acetate-co-divinylbenzene]; Poly[styrene-co-3-carboxymethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene]; Poly[styrene-co-3-carboxymethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene]; Poly[styrene-co-3-carboxymethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium acetate-co-divinylbenzene]; Poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene]; Poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene]; Poly[styrene-co-5-(4-vinylbenzylamino)-isophthalic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium acetate-co-divinylbenzene]; Poly[styrene-co-(4-vinylbenzylamino)-acetic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene]; Poly[styrene-co-(4-vinylbenzylamino)-acetic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene]; Poly[styrene-co-(4-vinylbenzylamino)-acetic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium acetate-co-divinylbenzene]; Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium chloride-co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium chloride-co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium sulfate-co-vinylbenzylmethylmorpholinium sulfate-co-vinylbenzyltriphenylphosphonium sulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium sulfate-co-vinylbenzylmethylmorpholinium sulfate-co-vinylbenzyltriphenylphosphonium sulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium acetate-co-vinylbenzylmethylmorpholinium acetate-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium acetate-co-vinylbenzylmethylmorpholinium acetate-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylmorpholinium sulfate-co-vinylbenzyltriphenylphosphonium sulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylmorpholinium sulfate-co-vinylbenzyltriphenylphosphonium sulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylmorpholinium acetate-co-vinylbenzyltriphenylphosphonium sulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylmorpholinium acetate-co-vinylbenzyltriphenylphosphonium sulfate-co-divinylbenzene) Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium sulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylmethylimidazolium nitrate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylmethylimidazolium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylmethylimidazolium sulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylmethylimidazolium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium sulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium sulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium sulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzylmethylimidazolium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium sulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzylmethylimidazolium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium sulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenesulfonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium sulfate-co-divinylbenzene); Poly(styrene-co-4-vinylbenzenephosphonic acid-co-vinylbenzyltriphenylphosphonium acetate-co-divinylbenzene); Poly(butyl-vinylimidazolium chloride-co-butylimidazolium sulfate-co-4-vinylbenzenesulfonic acid); Poly(butyl-vinylimidazolium sulfate-co-butylimidazolium sulfate-co-4-vinylbenzenesulfonic acid); Poly(benzyl alcohol-co-4-vinylbenzyl alcohol sulfonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzyl alcohol); and Poly(benzyl alcohol-co-4-vinylbenzyl alcohol sulfonic acid-co-vinylbenzyltriphenylphosphonium sulfate-co-divinylbenzyl alcohol) The method according to Embodiment 1, selected from the group consisting of

[0374] 52. The method according to any one of Embodiments 1 to 51, wherein the polymer is substantially insoluble in water or an organic solvent.

[0375] 53. The method according to Embodiment 1, wherein the catalyst comprises a solid support, an acidic site bonded to the solid support, and an ionic site bonded to the solid support.

[0376] 54. The method according to embodiment 53, wherein the solid support contains a substance, and the substance is selected from the group consisting of carbon, silica, silica gel, alumina, magnesia, titania, zirconia, clay, magnesium silicate, silicon carbide, zeolite, ceramics, and any combination thereof.

[0377] 55. The method according to embodiment 53 or 54, wherein each acidic site has at least one Bronsted-Lowry acid.

[0378] 56. The method according to any one of embodiments 53 to 55, wherein each ionic site independently has at least one nitrogen-containing cationic group or at least one phosphorus-containing cationic group, or a combination thereof.

[0379] 57. The method according to any one of embodiments 53 to 55, wherein the catalyst has a catalyst activity loss of less than 1% per cycle.

[0380] 58. The method according to any one of embodiments 1 to 57, wherein the one or more sugars are one or more monosaccharides and / or disaccharides.

[0381] 59. The method according to any one of embodiments 1 to 57, wherein the one or more sugars are one or more C5 or C6 monosaccharides (e.g., one or more C5 monosaccharides or one or more C6 monosaccharides).

[0382] 60. The method according to any one of embodiments 1 to 57, wherein the one or more sugars are selected from glucose, galactose, mannose, lactose, fructose, xylose, arabinose (e.g., one or more sugars selected from glucose, galactose, mannose, lactose, or e.g., one or more sugars selected from fructose, xylose, arabinose), or their corresponding sugar alcohols.

[0383] 61. The method according to any one of embodiments 1 to 52, comprising combining two or more sugars and a polymer catalyst to produce one or more oligosaccharides.

[0384] 62. The method according to embodiment 61, wherein two or more sugars are selected from glucose, galactose, mannose, and lactose (for example, glucose and galactose).

[0385] 63. The method according to any one of embodiments 1 to 52, wherein the weight ratio of the polymer catalyst to one or more sugars is from about 0.1 g / g to about 50 g / g (for example, from about 0.1 g / g to about 5 g / g, from about 0.5 g / g to about 1.0 g / g, from about 0.1 g / g to about 0.6 g / g, from about 0.2 g / g to about 0.5 g / g, or from about 0.25 g / g to about 0.5 g / g).

[0386] 64. The method according to any one of embodiments 1 to 63, wherein the reaction mixture comprises an aqueous solvent.

[0387] 65. The method according to embodiment 68, wherein the aqueous solvent is less than about 50% (by mass) of the reaction mixture, for example, less than about 40%, less than about 30%, less than about 25%, less than about 20%, less than about 15%, less than about 10%, or less than about 5%, or from about 5% to about 25%, or from about 10% to about 20%, or from about 10% to about 50%, for example, from about 15% to about 40%, from about 20% to about 35%, or from about 25% to about 30%.

[0388] 66. The method according to embodiment 64 or 65, further comprising removing at least a portion of the aqueous solvent from the reaction mixture (for example, by suction filtration, etc., removing at least any one of about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, about 97%, about 99%, or about 100%).

[0389] 67. At 3 hours after the step of combining one or more sugars and the catalyst, the degree of polymerization (DP) distribution of the oligosaccharides with respect to one or more oligosaccharides is DP2 = 0% to 40%, for example, less than 40%, less than 30%, less than 20%, less than 10%, less than 5%, or less than 2% or from 10% to 30% or from 15% to 25%, DP3 = 0% to 20%, for example less than 15%, less than 10%, less than 5%, or 5% to 15%, and DP4 is greater than 15%, greater than 20%, greater than 30%, greater than 40%, greater than 50%, or 15% to 75%, 20% to 40% or 25% to 35%, the method according to any one of Embodiments 1 to 66.

[0390] 68. The method according to any one of Embodiments 1 to 67, wherein the degree of polymerization (DP) distribution of the oligosaccharide with respect to one or more oligosaccharides 3 hours after the step of combining one or more sugars and a catalyst is any one of Entries (1) to (179) in Table 1.

[0391] 69. The method according to any one of Embodiments 1 to 68, wherein the conversion yield to one or more oligosaccharides, which is DP2, 3 hours after the step of combining one or more sugars and a catalyst is greater than about 50% (for example, greater than about 55%, greater than about 60%, greater than about 65%, greater than about 70%, greater than about 75%, greater than about 80%, greater than about 85%, greater than about 90%, greater than about 95%, or greater than about 98%).

[0392] 70. The method according to any one of Embodiments 1 to 69, wherein the conversion yield to one or more oligosaccharides that are DP2 3 hours after the step of combining one or more sugars and a catalyst is greater than 30% (for example, greater than 35%, greater than 40%, greater than 45%, greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90%, greater than 95%, or greater than 98%).

[0393] 71. The method according to any one of Embodiments 1 to 70, wherein the amount of sugar degradation products 3 hours after the step of combining one or more sugars and a catalyst is less than about 10% (for example, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, less than about 1%, less than about 0.75%, less than about 0.5%, less than about 0.25%, or less than about 0.1%), for example any one or combination of about 10% less of 1,6 - anhydroglucose (levoglucosan), 5 - hydroxymethylfurfural, 2 - furfuraldehyde, acetic acid, formic acid, levulinic acid and / or humin.

[0394] 72. The method according to any one of embodiments 1 to 71, further comprising the step of isolating one or more oligosaccharides.

[0395] 73. The method according to embodiment 72, wherein the step of isolating one or more oligosaccharides comprises separating at least a part of one or more oligosaccharides from at least a part of the catalyst (e.g., by suction filtration).

[0396] 74. The method according to embodiment 73, wherein the step of isolating one or more oligosaccharides further comprises separating at least a part of one or more oligosaccharides from at least a part of any unreacted sugar (e.g., by chromatography).

[0397] 75. The method according to embodiment 74, wherein the method is repeated by a continuous batch method, and the separated catalyst is reused by further contacting it with one or more sugars.

[0398] 76. The method according to embodiment 75, wherein the catalyst is reused at least 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 times.

[0399] 77. The method according to embodiment 76, wherein when the catalytic activity of the catalyst is compared under the same conditions as before reuse, it retains at least 80% of its activity (e.g., at least 90%, 95%, 96%, 97%, 98%, or 99% of its activity) after 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 times of reuse.

[0400] 78. The method according to any one of embodiments 72 to 74, wherein the method is carried out as a continuous method, and the steps of combining one or more sugars and the catalyst and isolating one or more oligosaccharides are carried out simultaneously.

[0401] 79. a) A step of combining one or more sugars and a catalyst to form a reaction mixture for producing one or more oligosaccharides, The catalyst comprises a plurality of acidic monomers and a plurality of cationic monomers linked to form a polymer backbone, or A step in which a solid-supported catalyst comprises a solid support, a plurality of acidic sites bonded to the solid support, and a plurality of ionic sites bonded to the solid support, b) isolating one or more oligosaccharides and the catalyst from the reaction mixture, and c) combining one or more additional sugars with the isolated catalyst to form a further reaction mixture that produces one or more additional oligosaccharides A method for producing one or more oligosaccharides, comprising:

[0402] 80. The method according to embodiment 79, wherein the step of isolating one or more oligosaccharides from the reaction mixture comprises separating at least a portion of the one or more oligosaccharides from i) at least a portion of the catalyst (e.g., by suction filtration) and ii) at least a portion of any unreacted sugar (e.g., by chromatography).

[0403] 81. The method according to embodiment 79 or 80, wherein the step of isolating the catalyst from the reaction mixture comprises separating at least a portion of the polymeric catalyst (e.g., by suction filtration) from at least a portion of the one or more oligosaccharides and at least a portion of any unreacted sugar.

[0404] 82. The method according to any one of embodiments 79 to 81, wherein after step c), steps b) and c) are repeated at least once (e.g., at least 2, 3, 4, 5, 6, 7, 8, 9 or 10 times).

[0405] 83. The method according to any one of embodiments 79 to 82, wherein the catalyst retains at least 80% of its activity (e.g., at least 90%, 95%, 96%, 97%, 98% or 99% of its activity) after being isolated 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 times when comparing its catalytic activity under the same conditions as before reuse.

[0406] 84. The method according to any one of embodiments 1 to 83, wherein the temperature at which one or more sugars and a catalyst are combined is maintained at about 60 to about 120 degrees Celsius (for example, about 80 to about 115, about 90 to about 110, or about 95 to about 105).

[0407] 85. The method according to any one of embodiments 1 to 84, wherein the combined one or more sugars and catalyst are reacted for at least 1 hour (for example, at least 2 hours, 3 hours, 4 hours, 6 hours, 8 hours, 16 hours, 24 hours, 36 hours, or 48 hours, for example 1 to 24 hours, 2 to 12 hours, 3 to 6 hours).

[0408] 86. An oligosaccharide or oligosaccharide composition obtained by the method according to any one of embodiments 1 to 85.

[0409] 87. Use of a polymeric catalyst (for example, any one of the polymeric catalysts described herein) comprising a plurality of acidic monomers and a plurality of cationic monomers for preparing one or more oligosaccharides from one or more sugars.

[0410] 88. Use of a solid-supported catalyst (for example, any one of the solid-supported catalysts described herein) comprising a plurality of acidic sites and a plurality of cationic sites for preparing one or more oligosaccharides from one or more sugars.

[0411] 89. A step of combining a feedstock sugar and a catalyst to form a reaction mixture, wherein the feedstock sugar contains an α-1,4 bond, and the catalyst comprises an acidic monomer and an ionic monomer linked to form a polymer backbone, or the catalyst comprises a solid support, an acidic site bonded to the solid support, and an ionic site bonded to the solid support, and Converting at least a part of the α-1,4 linkages in the feedstock sugar into one or more non-α-1,4 linkages selected from the group consisting of β-1,4 linkages, α-1,3 linkages, β-1,3 linkages, α-1,6 linkages, and β-1,6 linkages to produce an oligosaccharide composition from at least a part of the reaction mixture A method for producing an oligosaccharide composition, comprising:

[0412] 90. a) Combining one or more sugars and a catalyst to produce a first product mixture, wherein the first product mixture comprises a first oligosaccharide composition and a residual catalyst; b) Isolating at least a part of the residual catalyst from the product mixture; and c) Combining one or more additional sugars and the isolated residual catalyst to produce a further product mixture, wherein the further product mixture comprises a further oligosaccharide composition, and the catalytic activity of the isolated residual catalyst in the production of the further oligosaccharide composition is at least 30% of the catalytic activity of the catalyst in the production of the first oligosaccharide composition. A method for producing an oligosaccharide composition, comprising:

[0413] 91. a) Combining one or more sugars and a catalyst to produce a first product mixture, wherein the first product mixture comprises a first oligosaccharide composition and a residual catalyst, and the molar selectivity of the first oligosaccharide composition is at least 85%; b) Isolating at least a part of the residual catalyst from the first product mixture; c) Combining one or more additional sugars and the isolated residual catalyst to produce a further product mixture, wherein the further product mixture comprises a further oligosaccharide composition, and the catalytic activity of the isolated catalyst in the production of the further oligosaccharide composition is at least 30% of the catalytic activity of the catalyst in the production of the first oligosaccharide composition. A method for producing an oligosaccharide composition, comprising

[0414] 92. The method according to any one of embodiments 90 to 92, wherein the catalyst comprises an acidic monomer and an ionic monomer linked to form a polymer backbone, or The method according to embodiment 90 or 91, wherein the catalyst comprises a solid support, an acidic site bonded to the solid support, and an ionic site bonded to the solid support.

[0415] 93. The method according to any one of embodiments 90 to 92, wherein at least a part of the catalyst is isolated from the first product mixture by filtration or phase separation, or a combination thereof.

[0416] 94. The method according to any one of embodiments 90 to 93, wherein the selectivity of the additional oligosaccharide composition is at least 85%.

[0417] 95. The method according to any one of embodiments 90 to 94, wherein at least 10% of the first oligosaccharide composition has a degree of polymerization of 3 to 25.

[0418] 96. The method according to any one of embodiments 90 to 95, wherein at least 10% of the additional oligosaccharide composition has a degree of polymerization of 3 to 25.

[0419] 97. The method according to any one of embodiments 90 to 96, wherein at least 10% of the first oligosaccharide composition has a number average molecular weight of 230 to 10,000 g / mol.

[0420] 98. The method according to any one of embodiments 90 to 97, wherein at least 10% of the additional oligosaccharide composition has a number average molecular weight of 230 to 10,000 g / mol.

[0421] 99. A step of combining one or more sugars and a catalyst to produce an oligosaccharide composition, wherein the molar selectivity of the oligosaccharide composition is at least 85%, The catalyst comprises acidic monomers and ionic monomers linked to form the polymer backbone, or The catalyst comprises a solid support, acidic sites bonded to the solid support, and ionic sites bonded to the solid support, step A method for producing an oligosaccharide composition, comprising

[0422] 100. A step of combining an oligosaccharide composition with one or more functionalized compounds to produce a functionalized oligosaccharide composition, wherein The one or more functionalized compounds are independently selected from the group consisting of carboxylic acids, sugar alcohols, amino acids, amino sugars, alcohols, sulfates, and phosphates, step The method according to embodiment 99, further comprising

[0423] 101. A step of combining one or more sugars with a catalyst and one or more functionalized compounds to produce a functionalized oligosaccharide composition, wherein The one or more functionalized compounds are independently selected from the group consisting of carboxylic acids, sugar alcohols, amino acids, amino sugars, alcohols, sulfates, and phosphates, and the method for producing a functionalized oligosaccharide composition comprising the step.

[0424] 102. The method according to embodiment 101, wherein the molar selectivity of the functionalized oligosaccharide composition is at least 85%.

[0425] 103. The method according to any one of embodiments 90 to 102, wherein the one or more sugars are independently selected from the group consisting of glucose, galactose, xylose, arabinose, fructose, mannose, lactose, maltose, ribose, allose, fucose, glyceraldehyde, and rhamnose.

[0426] 104. The method according to any one of embodiments 100 to 103, wherein the one or more functionalized compounds are independently selected from the group consisting of glucosamine, galactosamine, lactic acid, acetic acid, citric acid, pyruvic acid, succinic acid, glutamic acid, aspartic acid, glucuronic acid, butyric acid, itaconic acid, malic acid, maleic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, adipic acid, isobutyric acid, formic acid, levulinic acid, valeric acid, isovaleric acid, sorbitol, xylitol, arabinitol, glycerol, erythritol, mannitol, galactitol, fucitol, iditol, inositol, volemitol, lactitol, ethanol, propanol, butanol, pentanol, hexanol, propanediol, butanediol, pentanediol, sulfate, and phosphate.

[0427] 105. The method according to any one of embodiments 99, 100, or 102 to 104, wherein at least 10% of the oligosaccharide composition has a degree of polymerization of 3 to 25.

[0428] 106. The method according to any one of embodiments 100 to 105, wherein at least 10% of the functionalized oligosaccharide composition has a degree of polymerization of 3 to 25.

[0429] 107. The method according to any one of embodiments 99, 100, or 102 to 105, wherein at least 10% of the oligosaccharide composition has a number average molecular weight of 230 to 10,000 g / mol.

[0430] 108. The method according to any one of embodiments 100 to 107, wherein at least 10% of the functionalized oligosaccharide composition has a number average molecular weight of 230 to 10,000 g / mol.

[0431] 109. An oligosaccharide composition comprising monosaccharide monomers linked by glycosidic bonds wherein the monosaccharide monomers are independently selected from the group consisting of C5 monosaccharides and C6 monosaccharides, and Each glycosidic bond is independently selected from the group consisting of α-1,4 bond, α-1,2 bond, β-1,2 bond, α-1,3 bond, β-1,3 bond, β-1,4 bond, α-1,6 bond and α-1,6 bond, At least 10% of the oligosaccharide composition has a degree of polymerization of at least 3, At least a part of the oligosaccharide composition contains at least two different glycosidic bonds, Oligosaccharide composition.

[0432] 110. The oligosaccharide composition according to embodiment 109, wherein the monosaccharide monomer is independently selected from the group consisting of glucose, galactose, xylose, arabinose, fructose, mannose, ribose, allose, fucose, glyceraldehyde and rhamnose.

[0433] 111. The monosaccharide monomers linked by glycosidic bonds form an oligomer backbone, and the oligomer backbone is optionally substituted by one or more pendant functional groups independently selected from the group consisting of carboxylic acid, sugar alcohol, amino acid, amino sugar, alcohol, sulfate and phosphate. The oligosaccharide composition according to embodiment 109 or 110.

[0434] 112. The monosaccharide monomers linked by glycosidic bonds form an oligomer backbone, and at least a part of the oligosaccharide composition further contains one or more crosslinkable functional groups, Each crosslinkable functional group independently links one of the oligomer backbones to an additional monosaccharide monomer, disaccharide, or additional oligomer backbone, The oligosaccharide composition according to any one of embodiments 109 to 111, wherein one or more crosslinkable functional groups are independently selected from the group consisting of polyol, polycarboxylic acid and amino acid.

[0435] 113. The oligosaccharide composition according to embodiment 112, wherein each additional oligomer backbone is optionally independently substituted by one or more pendant functional groups independently selected from the group consisting of carboxylic acid, sugar alcohol, amino acid, amino sugar, alcohol, sulfate, and phosphate.

[0436] 114. The oligosaccharide composition according to any one of embodiments 111 to 113, wherein the one or more pendant functional groups are independently selected from the group consisting of glucosamine, galactosamine, citric acid, succinic acid, glutamic acid, aspartic acid, glucuronic acid, butyric acid, itaconic acid, malic acid, maleic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, adipic acid, isobutyric acid, formic acid, levulinic acid, valeric acid, isovaleric acid, sorbitol, xylitol, arabinitol, glycerol, erythritol, mannitol, galactitol, fucitol, iditol, inositol, volemitol, lactitol, ethanol, propanol, butanol, pentanol, hexanol, propanediol, butanediol, pentanediol, sulfate, and phosphate.

[0437] 115. The oligosaccharide composition according to any one of embodiments 112 to 114, wherein the one or more crosslinkable functional groups are independently selected from the group consisting of glucosamine, galactosamine, lactic acid, acetic acid, citric acid, pyruvic acid, succinic acid, glutamic acid, aspartic acid, glucuronic acid, itaconic acid, malic acid, maleic acid, adipic acid, sorbitol, xylitol, arabinitol, glycerol, erythritol, mannitol, galactitol, fucitol, iditol, inositol, volemitol, lactitol, propanediol, butanediol, pentanediol, sulfate, and phosphate.

[0438] 116. The oligosaccharide composition according to any one of embodiments 109 to 115, wherein at least 10% of the oligosaccharide composition has a number average molecular weight of 230 to 10,000 g / mol.

[0439] 117. A step of contacting an α-1,4 polysaccharide with a catalyst, wherein the catalyst comprises an acidic monomer and an ionic monomer linked to form a polymer main chain, or the catalyst comprises a solid support, an acidic site bonded to the solid support, and an ionic site bonded to the solid support, and a step of converting at least a part of the α-1,4 linkages in the α-1,4 polysaccharide into one or more non-α-1,4 linkages selected from the group consisting of α-1,2 linkages, β-1,2 linkages, α-1,3 linkages, β-1,3 linkages, β-1,4 linkages, α-1,6 linkages, and β-1,6 linkages to produce a polysaccharide having a mixed linking group A method for converting an α-1,4 polysaccharide into a polysaccharide having a mixed linking group, comprising the above steps.

Examples

[0440] The following examples are provided by way of illustration and are not intended to limit the present invention.

[0441] Unless otherwise indicated, commercially available reagents were obtained from Sigma-Aldrich, St. Louis, MO, USA and purified prior to use according to the guidelines of Perrin and Armarego. See Perrin, D. D. and Armarego, W. L. F., Purification of Laboratory Chemicals, 3rd ed.; Pergamon Press, Oxford, 1988. The nitrogen gas used in chemical reactions was of ultra-high purity grade and dried by passing it through a drying tube containing phosphorus pentoxide. Unless otherwise indicated, all non-aqueous reagents were transferred under an inert atmosphere using a syringe or Schlenk flask. Organic solutions were concentrated under reduced pressure using a Buchi rotary evaporator. If necessary, chromatographic purification of the reactants or products was carried out using forced-flow chromatography on 60-mesh silica gel according to the method described by Still et al. (see J. Org. Chem., Vol. 43: 2923 (1978)). Thin-layer chromatography (TLC) was carried out using glass plates coated with silica. If necessary, visualization of the developed chromatogram was carried out using either cerium molybdate (i.e., Hanessian) staining or KMnO 4 staining. Fourier transform infrared (FTIR) spectroscopy of solid samples was carried out using a Perkin-Elmer 1600 instrument equipped with a horizontal attenuated total reflection (ATR) accessory using zinc selenide (ZnSe) crystals.

[0442] The moisture content of the reagents was determined using a Mettler-Toledo MJ-33 moisture analysis balance with a sample size of 0.5 - 1.0 g. All moisture contents were determined as the average weight % loss on drying obtained from three measurements.

[0443] The soluble sugar and oligosaccharide contents of the reaction products were determined by combining high performance liquid chromatography (HPLC) and spectrophotometry. HPLC determination of soluble sugars and oligosaccharides was performed on a Hewlett-Packard 1100 series instrument equipped with a refractive index (RI) detector using a 30 cm × 7.8 mm BioRad Aminex HPX-87P column with water as the mobile phase. The sugar column was protected by both a lead-exchanged sulfonated-polystyrene guard column and a trialkylammonium hydroxide anion exchange guard column. All HPLC samples were filter-sterilized through a 0.2 μm syringe filter prior to injection. Sample concentrations were determined by reference to a calibration generated from a standard solution containing known concentrations of glucose, xylose, arabinose, galactose, and glucooligosaccharides.

[0444] The formation of soluble sugar degradation products was determined by high performance liquid chromatography (HPLC) on a Hewlett-Packard 1100 series instrument equipped with a refractive index (RI) detector using a 30 cm × 7.8 mm BioRad Aminex HPX-87H column with 50 mM sulfuric acid as the mobile phase. The sugar column was protected by a sulfonated-polystyrene guard column, and all HPLC samples were filter-sterilized through a 0.2 μm syringe filter prior to injection. Sample concentrations were determined by reference to a calibration generated from a standard solution containing formic acid, acetic acid, levulinic acid, 5-hydroxymethylfurfural, and 2-furaldehyde.

[0445] The number-average degree of polymerization (DP) of the oligosaccharides, containing monomer units of anhydro sugars of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 to 15, and over 15, was determined as the number-average of the species. The relative concentrations of the oligosaccharides corresponding to these various DPs were determined by high performance liquid chromatography (HPLC) using a 30 cm × 7.8 mm BioRad Aminex HPX-87A column with water as the mobile phase and a Hewlett-Packard 110 series instrument equipped with a refractive index (RI) detector. The analytical column was protected by a sulfonated-polystyrene protected column with coordinated silver, and all HPLC samples were precisely filtered using a 0.2 μm syringe filter prior to injection.

[0446] The presence of glycosidic linkages was determined by proton nuclear magnetic resonance ( 1 1H-NMR). In the analysis, the oligosaccharide sample was dried under vacuum at 70 °C, redissolved in deuterium oxide, equilibrated at room temperature for 2 hours, and then the cycle of drying under vacuum and redissolving in deuterium oxide was repeated. The proton NMR spectrum was obtained at 400 MHz, and the peak assignments were made according to Roslund, M.U. et al., Carb.Res., Vol. 343, pp. 101 - 112 (2008). Further decomposition of the peaks and identification of the (1,4) linkages were performed by J-resolved (JRES) NMR.

[0447] The conversion rate X(t) of the monomer (DP1) sugar at time t was

[0448] [Number] determined according to the formula, where mol(DP1,t) represents the total number of moles of monosaccharides present in the reactants at time t, and mol(DP1,0) represents the total number of moles of monosaccharides initially charged to the reactants. Similarly, the yield to the oligosaccharides of a given DP was

[0449] [Number] Determined according to the formula, where mol(DPn,t) represents the total molar equivalents of the species with DP = n, measured in units of molar equivalents of monosaccharides. The total yield to oligosaccharides with DP>1 was

[0450] [Number] Determined according to the formula, and the total yield to oligosaccharides with DP>2 was

[0451] [Number] Determined. The molar yield to the sugar degradation products was determined in the same way as the molar yield to the oligosaccharides, where the molar amounts were measured as molar equivalents of monosaccharides. Finally, the molar selectivity to a given product species was determined as the ratio of the yield of that species to the sugar conversion rate, i.e., S(t)=Y(t) / X(t).

[0452] The formation of unwanted non-carbohydrate by-products such as polyfurans, solid humins, and other condensation products was determined by analogy from the molar balance of the reaction. Specifically, the molar yield to the unwanted by-products was determined as the arithmetic difference between the monosaccharide conversion rate - (minus) the sum of the yields to all quantifiable species. Similarly, the total molar yield to carbohydrates was determined by hydrolyzing a given oligosaccharide mixture to its constituent monosaccharides under acid dilution conditions (in 2% - 4% sulfuric acid, incubated at 121 degrees Celsius for 1 hour) at high temperature, measuring the number of moles of the resulting monosaccharides, and correcting it with a standard monomer control solution treated under the same hydrolysis conditions.

[0453] The viscosity of the oligosaccharide mixture was determined using a Brookfield viscometer placed on a temperature-controlled water bath used to set the temperature of the solution measured from room temperature to approximately 95 degrees Celsius. The acid content of the catalyst sample and the aqueous solution was determined using a Hana Instruments 902-C automatic titrator using sodium hydroxide as the titrant calibrated with a standard solution of potassium hydrogen phthalate (KHP).

[0454] The concentration of the liquid sample was carried out using a rotary evaporator unit of the Buchi r124 series. For the oligosaccharide solution in water, a bath temperature of about 40 - 60 degrees Celsius was used. The vacuum pressure was set to 50 - 150 mTorr with an oil-immersed pump, and this pump was protected by an acetone-dry ice trap to prevent the volatile solvent from being sucked into the pump system.

[0455] Freeze-drying of the oligosaccharide sample for analytical use was carried out by coating the wall of a 100 mL round-bottom flask (RBF) with approximately 2 grams of the oligosaccharide solution at an initial concentration of 60 - 70 wt% of the dissolved solid. The loaded flask was placed in a freezer at -20 degrees Celsius for 2 hours, and then the flask was quickly removed to a room temperature environment and evacuated. The static pressure was set to 50 - 150 mTorr with an oil-immersed pump, and this pump was protected by an acetone-dry ice trap to prevent the volatile solvent from being sucked into the pump system. Usually, the freeze-pump cycle was performed 3 times continuously.

[0456] Preparation of Polymer Substances [Example 1] Preparation of Poly[styrene-co-vinylbenzyl chloride-co-divinylbenzene] 250.0 mL of deionized H at 0 °C 2To a 500 mL round-bottom flask (RBF) containing a stirred solution of 1.08 g of poly(vinyl alcohol) in O, a solution containing 50.04 g (327.9 mmol) of vinylbenzyl chloride (a mixture of 3- and 4-isomers), 10.13 g (97.3 mmol) of styrene, 1.08 g (8.306 mmol) of divinylbenzene (DVB, a mixture of 3- and 4-isomers), and 1.507 g (9.2 mmol) of azobisisobutyronitrile (AIBN) in a 1:1 (volume ratio) mixture of 150 mL of benzene / tetrahydrofuran (THF) at 0 °C was added slowly. The mixture was stirred at 0 °C for 2 hours until homogeneous, then the reaction flask was transferred to an oil bath and the reaction temperature was raised to 75 °C and the mixture was stirred vigorously for 28 hours. The resulting polymer beads were vacuum filtered using a glass funnel with a frit to recover the polymer product. The beads were washed repeatedly with 20 (volume)% methanol, THF, and MeOH in water and dried overnight at 50 °C under reduced pressure to obtain 59.84 g of polymer. Sieves with mesh sizes 100, 200, and 400 were used to separate the polymer beads by size.

[0457] [Example 2] Preparation of Poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene] Poly(styrene-co-vinylbenzyl chloride-co-divinylbenzene)(Cl - Poly(styrene-co-vinylbenzyl chloride-co-divinylbenzene) (Cl density = ~4.0 mmol / g, 50 g, 200 mmol) was charged into a 500 mL three-necked flask (TNF) equipped with a mechanical stirrer, a dry nitrogen line, and a purge valve. Dry dimethylformamide (185 ml) was added to the flask (via a cannula under N 2 to form a viscous slurry of the polymer resin. Next, 1-methylimidazole (36.5 g, 445 mmol) was added and the mixture was stirred at 95 °C for 8 hours. After cooling, the reaction mixture was filtered using a glass funnel with a frit under vacuum, washed successively with deionized water and ethanol, and finally air dried.

[0458] The chemical functionalization of the polymer material, expressed as the number of millimoles of functional groups per gram (mmol / g) of the dry polymer resin, was measured by ion-exchange titration. To determine the cation-exchangeable acidic protons, a polymer resin of known dry mass was added to a saturated aqueous sodium chloride solution and titrated with a standard sodium hydroxide solution to the endpoint of phenolphthalein. To determine the content of chloride ions exchangeable as anions, a polymer resin of known dry mass was added to an aqueous sodium nitrate solution and neutralized with sodium carbonate. The resulting mixture was titrated with a standard solution of silver nitrate to the endpoint of potassium chromate. In the case of polymer substances where the exchangeable anion is not chloride, the substance was first stirred in an aqueous hydrochloric acid solution and then repeatedly washed with water until the effluent became neutral (as determined by pH paper) to treat the polymer. The chemical functionalization of the polymer resin with methylimidazolium chloride groups was determined to be 2.60 mmol / g by gravimetry and 2.61 mmol / g by titration.

[0459] [Example 3] Preparation of Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene] Into a 500 mL flask equipped with a magnetic stirrer and a condenser, poly[styrene-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene] (63 g) was charged. Under stirring, concentrated sulfuric acid (>98% w / w, H 2 SO 4 , 300 mL) was gradually added, resulting in the formation of a dark red resin slurry. The slurry was stirred at 85 °C for 4 hours. After cooling to room temperature, the reaction mixture was filtered using a glass funnel with a frit under vacuum and then repeatedly washed with deionized water until the effluent became neutral as determined by pH paper. The sulfonated resin beads were finally washed with ethanol and air-dried. The chemical functionalization of the polymer resin with sulfonic acid groups was measured by titration according to the procedure of Example 2 and determined to be 1.60 mmol / g.

[0460] [Example 4] Preparation of poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene] Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene] (sample of Example 3) placed in a glass funnel with frit was repeatedly washed with 0.1 M HCl solution to ensure complete exchange of sulfate ions and Cl - ions. Next, the resin was washed with deionized water until the effluent became neutral as determined by pH paper. The resin was finally air-dried.

[0461] [Example 5] Preparation of poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium acetate-co-divinylbenzene] A suspension of poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene] (sample of Example 3) in 10% aqueous acetic acid solution was stirred at 60 °C for 2 hours to ensure complete exchange of sulfate ions and AcO - ions. The resin was filtered using a glass funnel with frit and then washed multiple times with deionized water until the effluent became neutral. The resin was finally air-dried.

[0462] [Example 6] Preparation of poly[styrene-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene] Poly(styrene-co-vinylbenzyl chloride-co-divinylbenzene) (Cl -(Density = ~4.0 mmol / g, 10 g, 40 mmol) was charged into a 250 three-necked flask (TNF) equipped with a mechanical stirrer, a dry nitrogen line, and a purge valve. Dry dimethylformamide (80 ml) was added to the flask (under N 2 via a cannula) and stirred to obtain a viscous resin slurry. Next, 1-ethylimidazole (4.3 g, 44.8 mmol) was added to the resin slurry and stirred at 95 °C for 8 hours. After cooling, the reaction mixture was filtered using a glass funnel with frit under vacuum, washed successively with deionized water and ethanol, and finally air-dried. Chemical functionalization of the polymer resin with ethylimidazolium chloride groups was measured by the titration method according to the procedure of Example 1 and determined to be 1.80 mmol / g.

[0463] [Example 7] Preparation of Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene] Poly[styrene-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene] (5 g) was charged into a 100 mL flask equipped with a magnetic stir bar and a condenser. Under stirring, concentrated sulfuric acid (>98% w / w, H 2 SO 4 , 45 mL) was gradually added, resulting in the formation of a dark red homogeneous resin slurry. The slurry was stirred at 95 - 100 °C for 6 hours. After cooling, the reaction mixture was filtered using a glass funnel with frit under vacuum and then repeatedly washed with deionized water until the effluent was neutral as determined by pH paper. The sulfonated beads were finally washed with ethanol and air-dried. Chemical functionalization of the polymer with sulfonic acid groups was measured by the titration method according to the procedure of Example 2 and determined to be 1.97 mmol / g.

[0464] [Example 8] Preparation of Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene] Poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene] resin beads (sample of Example 7) contained in a fritted glass funnel were washed multiple times with 0.1 M HCl solution to ensure complete exchange of sulfate ions and Cl - . Next, the resin was washed with deionized water until the effluent became neutral as determined by pH paper. The resin was finally washed with ethanol and air-dried.

[0465] [Example 9] Preparation of Poly[styrene-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene] Into a 100 mL flask equipped with a magnetic stir bar and a condenser, poly(styrene-co-vinylbenzyl chloride-co-divinylbenzene) (Cl - density = ~4.0 mmol / g, 10 g, 40 mmol) was charged. Chloroform (50 ml) was added to the flask and stirred to form a resin slurry. Next, imidazole (2.8 g, 41.13 mmol) was added to the resin slurry and stirred at 40 °C for 18 h. After completion of the reaction, the reaction mixture was filtered using a fritted glass funnel under vacuum, washed successively with deionized water and ethanol, and finally air-dried. Chemical functionalization with imidazolium chloride groups of the polymer resin was measured by titration according to the procedure of Example 2 and determined to be 2.7 mmol / g.

[0466] [Example 10] Preparation of Poly[styrene-co-4-vinylbenzenesulfonic acid-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium sulfate-co-divinylbenzene] Into a 100 mL flask equipped with a magnetic stir bar and a condenser, poly[styrene-co-1-(4-vinylbenzyl)-3H-imidazol-1-ium chloride-co-divinylbenzene] (5 g) was charged. Concentrated sulfuric acid (>98% w / w, H 2 SO 4 , 80 mL) was slowly added to the flask and stirred to form a dark red resin slurry. The slurry was stirred at 95 °C for 8 hours. After cooling, the reaction mixture was filtered using a glass funnel with a frit under vacuum and then washed repeatedly w...

Claims

1. a) combining one or more sugars with a catalyst to produce a first product mixture, the first product mixture comprising a first oligosaccharide composition and residual catalyst; b) isolating at least a portion of the residual catalyst from the product mixture; and c) combining the additional one or more sugars with the isolated residual catalyst to produce a further product mixture, the further product mixture comprises a further oligosaccharide composition; the catalytic activity of the isolated residual catalyst in producing the further oligosaccharide composition is at least 30% of the catalytic activity of the catalyst in producing the first oligosaccharide composition.

2. A method for producing an oligosaccharide composition comprising:

2. a) combining one or more sugars with a catalyst to produce a first product mixture, the first product mixture comprising a first oligosaccharide composition and residual catalyst; a molar selectivity of the first oligosaccharide composition is at least 85%. b) isolating at least a portion of the residual catalyst from the first product mixture; and c) combining the additional one or more sugars with the isolated residual catalyst to produce a further product mixture, the further product mixture comprises a further oligosaccharide composition; a catalytic activity of the isolated catalyst in producing the additional oligosaccharide composition is at least 30% of the catalytic activity of the catalyst in producing the first oligosaccharide composition.

2. A method for producing an oligosaccharide composition comprising:

3. the catalyst comprises acidic and ionic monomers linked to form a polymer backbone; or the catalyst comprises a solid support, acidic sites bound to the solid support, and ionic sites bound to the solid support; The method according to claim 1 or 2.

4. The process of any one of claims 1 to 3, wherein at least a portion of the catalyst is isolated from the first product mixture by filtration or phase separation, or a combination thereof.

5. The method according to any one of claims 1 to 4, wherein the selectivity for the further oligosaccharide composition is at least 85%.

6. The method according to any one of claims 1 to 5, wherein at least 10% of the first oligosaccharide composition has a degree of polymerization between 3 and 25.

7. The method according to any one of claims 1 to 6, wherein at least 10% of the further oligosaccharide composition has a degree of polymerization of between 3 and 25.

8. 8. The method according to claim 1, wherein at least 10% of the first oligosaccharide composition has a number average molecular weight of 230 to 10,000 g / mol.

9. The method according to any one of claims 1 to 8, wherein at least 10% of the further oligosaccharide composition has a number average molecular weight of 230 to 10,000 g / mol.

10. combining one or more sugars with a catalyst to produce an oligosaccharide composition, the molar selectivity of the oligosaccharide composition is at least 85%; the catalyst comprises acidic and ionic monomers linked to form a polymer backbone; or the catalyst comprises a solid support, acidic sites bound to the solid support, and ionic sites bound to the solid support; 2. A method for producing an oligosaccharide composition comprising:

11. combining the oligosaccharide composition with one or more functionalizing compounds to produce a functionalized oligosaccharide composition, the one or more functionalizing compounds are independently selected from the group consisting of carboxylic acids, sugar alcohols, amino acids, amino sugars, alcohols, sulfates, and phosphates. The method of claim 10 further comprising:

12. combining one or more sugars with a catalyst and one or more functionalizing compounds to produce a functionalized oligosaccharide composition; 1. A method for producing a functionalized oligosaccharide composition comprising the steps of: one or more functionalizing compounds independently selected from the group consisting of carboxylic acids, sugar alcohols, amino acids, amino sugars, alcohols, sulfates, and phosphates.

13. 13. The method of claim 12, wherein the molar selectivity of the functionalized oligosaccharide composition is at least 85%.

14. 14. The method of any one of claims 1 to 13, wherein the one or more sugars are independently selected from the group consisting of glucose, galactose, xylose, arabinose, fructose, mannose, lactose, maltose, ribose, allose, fucose, glyceraldehyde and rhamnose.

15. 15. The method of any one of claims 11 to 14, wherein the one or more functionalizing compounds are independently selected from the group consisting of glucosamine, galactosamine, lactic acid, acetic acid, citric acid, pyruvic acid, succinic acid, glutamic acid, aspartic acid, glucuronic acid, butyric acid, itaconic acid, malic acid, maleic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, adipic acid, isobutyric acid, formic acid, levulinic acid, valeric acid, isovaleric acid, sorbitol, xylitol, arabitol, glycerol, erythritol, mannitol, galactitol, fucitol, iditol, inositol, volemitol, lactitol, ethanol, propanol, butanol, pentanol, hexanol, propanediol, butanediol, pentanediol, sulfates, and phosphates.

16. 16. The method of any one of claims 10, 11, 14 or 15, wherein at least 10% of the oligosaccharide composition has a degree of polymerization between 3 and 25.

17. 16. The method according to any one of claims 11 to 15, wherein at least 10% of the functionalized oligosaccharide composition has a degree of polymerization between 3 and 25.

18. 17. The method of any one of claims 10, 11, or 14 to 16, wherein at least 10% of the oligosaccharide composition has a number average molecular weight of 230 to 10,000 g / mol.

19. 19. The method according to any one of claims 11 to 18, wherein at least 10% of the functionalized oligosaccharide composition has a number average molecular weight of 230 to 10,000 g / mol.

20. Monosaccharide monomers linked by glycosidic bonds An oligosaccharide composition comprising: the monosaccharide monomers are independently selected from the group consisting of C5 monosaccharides and C6 monosaccharides; each glycosidic bond is independently selected from the group consisting of an α-1,4 bond, an α-1,2 bond, a β-1,2 bond, an α-1,3 bond, a β-1,3 bond, a β-1,4 bond, an α-1,6 bond, and an α-1,6 bond; at least 10% of the oligosaccharide composition has a degree of polymerization of at least 3; An oligosaccharide composition, at least a portion of which comprises at least two different glycosidic linkages.

21. 21. The oligosaccharide composition of claim 20, wherein the monosaccharide monomers are independently selected from the group consisting of glucose, galactose, xylose, arabinose, fructose, mannose, ribose, allose, fucose, glyceraldehyde and rhamnose.

22. 22. The oligosaccharide composition of claim 20 or 21, wherein the monosaccharide monomers linked by glycosidic bonds form an oligomeric backbone, and the oligomeric backbone is optionally substituted with one or more pendant functional groups independently selected from the group consisting of carboxylic acids, sugar alcohols, amino acids, amino sugars, alcohols, sulfates and phosphates.

23. wherein the monosaccharide monomers linked by glycosidic bonds form an oligomeric backbone, and at least a portion of the oligosaccharide composition further comprises one or more crosslinkable functional groups; each crosslinkable functional group independently links one of the oligomeric backbones to an additional monosaccharide monomer, a disaccharide, or an additional oligomeric backbone; The oligosaccharide composition according to any one of claims 20 to 22, wherein the one or more crosslinkable functional groups are independently selected from the group consisting of polyols, polycarboxylic acids and amino acids.

24. 24. The oligosaccharide composition of claim 23, wherein each additional oligomeric backbone is independently optionally substituted with one or more pendant functional groups independently selected from the group consisting of carboxylic acids, sugar alcohols, amino acids, amino sugars, alcohols, sulfates and phosphates.

25. 25. The oligosaccharide composition of any one of claims 22 to 24, wherein the one or more pendant functional groups are independently selected from the group consisting of glucosamine, galactosamine, citric acid, succinic acid, glutamic acid, aspartic acid, glucuronic acid, butyric acid, itaconic acid, malic acid, maleic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, adipic acid, isobutyric acid, formic acid, levulinic acid, valeric acid, isovaleric acid, sorbitol, xylitol, arabitol, glycerol, erythritol, mannitol, galactitol, fucitol, iditol, inositol, volemitol, lactitol, ethanol, propanol, butanol, pentanol, hexanol, propanediol, butanediol, pentanediol, sulfate, and phosphate.

26. 26. The oligosaccharide composition of any one of claims 23 to 25, wherein the one or more crosslinkable functional groups are independently selected from the group consisting of glucosamine, galactosamine, lactic acid, acetic acid, citric acid, pyruvic acid, succinic acid, glutamic acid, aspartic acid, glucuronic acid, itaconic acid, malic acid, maleic acid, adipic acid, sorbitol, xylitol, arabitol, glycerol, erythritol, mannitol, galactitol, fucitol, iditol, inositol, volemitol, lactitol, propanediol, butanediol, pentanediol, sulfate and phosphate.

27. 27. The oligosaccharide composition according to any one of claims 20 to 26, wherein at least 10% of the oligosaccharide composition has a number average molecular weight of 230 to 10,000 g / mol.

28. contacting an α-1,4 polysaccharide with a catalyst, the catalyst comprises acidic monomers and ionic monomers linked to form a polymer backbone, or the catalyst comprises a solid support, acidic sites bound to the solid support, and ionic sites bound to the solid support; and converting at least a portion of the α-1,4 linkages in the α-1,4 polysaccharide to one or more non-α-1,4 linkages selected from the group consisting of α-1,2 linkages, β-1,2 linkages, α-1,3 linkages, β-1,3 linkages, β-1,4 linkages, α-1,6 linkages, and β-1,6 linkages to produce a polysaccharide having a mixture of linking groups.

2. A method for converting an α-1,4 polysaccharide into a polysaccharide having a mixture of linking groups, comprising:

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