WO2014031956A1 - Catalyseurs polymères et à support solide, et procédés de digestion de matériaux cellulosiques utilisant lesdits catalyseurs - Google Patents

Catalyseurs polymères et à support solide, et procédés de digestion de matériaux cellulosiques utilisant lesdits catalyseurs Download PDF

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WO2014031956A1
WO2014031956A1 PCT/US2013/056389 US2013056389W WO2014031956A1 WO 2014031956 A1 WO2014031956 A1 WO 2014031956A1 US 2013056389 W US2013056389 W US 2013056389W WO 2014031956 A1 WO2014031956 A1 WO 2014031956A1
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Prior art keywords
supported
carbon
sulfonic acid
acid
catalyst
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PCT/US2013/056389
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English (en)
Inventor
John M. GEREMIA
Brian M. Baynes
Jaouad Fichtali
Joseph ANDOH
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Midori Renewables, Inc.
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Priority claimed from US13/831,495 external-priority patent/US9238845B2/en
Application filed by Midori Renewables, Inc. filed Critical Midori Renewables, Inc.
Priority to EP13831228.5A priority Critical patent/EP2888044A4/fr
Priority to KR1020157007481A priority patent/KR20150047583A/ko
Priority to US14/423,697 priority patent/US20150202607A1/en
Priority to CN201380055050.3A priority patent/CN104736245B/zh
Priority to CA2922254A priority patent/CA2922254A1/fr
Publication of WO2014031956A1 publication Critical patent/WO2014031956A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
    • B01J31/0294—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by polar or ionic interaction with the substrate, e.g. glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
    • B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B01J31/10—Ion-exchange resins sulfonated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0057—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Xylans, i.e. xylosaccharide, e.g. arabinoxylan, arabinofuronan, pentosans; (beta-1,3)(beta-1,4)-D-Xylans, e.g. rhodymenans; Hemicellulose; Derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds

Definitions

  • the present disclosure relates generally to methods of producing sugars from biomass, and more specifically to methods of producing sugars from various biomass feedstocks using catalysts, such as polymeric catalysts or solid-supported catalysts.
  • ethanol biologicalethanol
  • cellulose or hemicellulose which are major constituents of plants.
  • the hydrolysis products which include sugars and simple carbohydrates, can then be subjected to further biological and/or chemical conversion to produce fuels or other commodity chemicals.
  • ethanol is utilized as a fuel or mixed into a fuel such as gasoline.
  • Major constituents of plants include, for example, cellulose (a polymer glucose, which is a six-carbon sugar), hemicellulose (a branched polymer of five- and six-carbon sugars), lignin, and starch.
  • Current methods for liberating sugars from lignocellulosic materials are inefficient on a commercial scale based on yields, as well as the water and energy used.
  • the present disclosure addresses this need by providing polymeric catalysts and solid-supported catalysts that can be used to digest hemicellulose and cellulose, including the crystalline domains of cellulose, in biomass.
  • the methods described herein using the catalysts can hydrolyze the cellulose and/or hemicellulose into one or more sugars, including monosaccharides and/or
  • the sugars may be used as a food agent, for example, as a sweetening or flavoring agent.
  • the sugars may be used for human consumption or for non-human consumption (e.g. , for pet consumption or as part of agricultural feed).
  • a polymeric catalyst that includes acidic monomers and ionic monomers connected to form a polymeric backbone, wherein each acidic monomer independently includes at least one Bronsted-Lowry acid, and wherein each ionic monomer independently includes at least one nitrogen-containing cationic group, at least one phosphorous- containing cationic group, or a combination thereof.
  • a solid-supported catalyst that includes a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support, wherein each acidic moiety independently includes at least one Bronsted-Lowry acid, and wherein each ionic moiety independently includes at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or a combination thereof;
  • a method of producing one or more sugars from softwood by: a) providing softwood; b) contacting the softwood with a catalyst to form a reaction mixture, wherein the catalyst is a polymeric catalyst or a solid-supported catalyst, wherein the polymeric catalyst includes acidic monomers and ionic monomers connected to form a polymeric backbone, wherein each acidic monomer independently includes at least one Bronsted-Lowry acid, and wherein each ionic monomer independently includes at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or a combination thereof, wherein the solid- supported catalyst includes a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support, wherein each acidic moiety independently includes at least one Bronsted-Lowry acid, and wherein each ionic moiety independently includes at least one nitrogen-containing cationic group, at least one phosphorous- containing cationic group, or
  • the softwood is pine. In other embodiments, the softwood is in a form selected from chips, sawdust, bark, and any combination thereof.
  • a method of producing one or more sugars from hardwood by: a) providing hardwood; b) contacting the hardwood with a catalyst to form a reaction mixture, wherein the catalyst is a polymeric catalyst or a solid-supported catalyst, wherein the polymeric catalyst includes acidic monomers and ionic monomers connected to form a polymeric backbone, wherein each acidic monomer independently includes at least one Bronsted-Lowry acid, and wherein each ionic monomer independently includes at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or a combination thereof, wherein the solid-supported catalyst includes a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support, wherein each acidic moiety independently includes at least one Bronsted-Lowry acid, and wherein each ionic moiety independently includes at least one nitrogen-containing cationic group, at least one phosphorous- containing cationic group, or a combination thereof
  • the hardwood is selected from birch, eucalyptus, aspen, maple, and any combination thereof. In other embodiments, the hardwood is in a form selected from chips, sawdust, bark, and any combination thereof.
  • a method of producing one or more sugars from cassava by: a) providing cassava; b) contacting the cassava with a catalyst to form a reaction mixture, wherein the catalyst is a polymeric catalyst or a solid-supported catalyst, wherein the polymeric catalyst includes acidic monomers and ionic monomers connected to form a polymeric backbone, wherein each acidic monomer independently includes at least one Bronsted-Lowry acid, and wherein each ionic monomer independently includes at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or a combination thereof, wherein the solid- supported catalyst includes a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support, wherein each acidic moiety independently includes at least one Bronsted-Lowry acid, and wherein each ionic moiety independently includes at least one nitrogen-containing cationic group, at least one phosphorous- containing cationic group
  • a method of producing one or more sugars from bagasse by: a) providing bagasse; b) contacting the bagasse with a catalyst to form a reaction mixture, wherein the catalyst is a polymeric catalyst or a solid-supported catalyst, wherein the polymeric catalyst includes acidic monomers and ionic monomers connected to form a polymeric backbone, wherein each acidic monomer independently includes at least one Bronsted-Lowry acid, and wherein each ionic monomer independently includes at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or a combination thereof, wherein the solid- supported catalyst includes a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support, wherein each acidic moiety independently includes at least one Bronsted-Lowry acid, and wherein each ionic moiety independently includes at least one nitrogen-containing cationic group, at least one phosphorous- containing cationic group, or
  • a method of producing one or more sugars from oil palm by: a) providing oil palm; b) contacting the oil palm with a catalyst to form a reaction mixture, wherein the catalyst is a polymeric catalyst or a solid-supported catalyst, wherein the polymeric catalyst includes acidic monomers and ionic monomers connected to form a polymeric backbone, wherein each acidic monomer independently includes at least one Bronsted-Lowry acid, and wherein each ionic monomer independently includes at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or a combination thereof, wherein the solid-supported catalyst includes a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support, wherein each acidic moiety independently includes at least one Bronsted-Lowry acid, and wherein each ionic moiety independently includes at least one nitrogen-containing cationic group, at least one phosphorous- containing cationic group, or
  • the oil palm is a palm oil waste material selected from empty fruit bunch, mesocarp fibre, and any combination thereof.
  • a method of producing one or more sugars from corn stover by: a) providing corn stover; b) contacting the corn stover with a catalyst to form a reaction mixture, wherein the catalyst is a polymeric catalyst or a solid-supported catalyst, wherein the polymeric catalyst includes acidic monomers and ionic monomers connected to form a polymeric backbone, wherein each acidic monomer independently includes at least one Bronsted-Lowry acid, and wherein each ionic monomer independently includes at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or a combination thereof, wherein the solid- supported catalyst includes a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support, wherein each acidic moiety independently includes at least one Bronsted-Lowry acid, and wherein each ionic moiety independently includes at least one nitrogen-containing cationic group, at least one phosphorous- containing cationic
  • a method of producing one or more sugars from food waste by: a) providing food waste; b) contacting the food waste with a catalyst to form a reaction mixture, wherein the catalyst is a polymeric catalyst or a solid-supported catalyst, wherein the polymeric catalyst includes acidic monomers and ionic monomers connected to form a polymeric backbone, wherein each acidic monomer independently includes at least one Bronsted-Lowry acid, and wherein each ionic monomer independently includes at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or a combination thereof, wherein the solid-supported catalyst includes a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support, wherein each acidic moiety independently includes at least one Bronsted-Lowry acid, and wherein each ionic moiety independently includes at least one nitrogen-containing cationic group, at least one phosphorous- containing cationic group, or
  • a method of producing one or more sugars from enzymatic digestion residuals by: a) providing enzymatic digestion residuals; b) contacting the enzymatic digestion residuals with a catalyst to form a reaction mixture, wherein the catalyst is a polymeric catalyst or a solid-supported catalyst, wherein the polymeric catalyst includes acidic monomers and ionic monomers connected to form a polymeric backbone, wherein each acidic monomer independently includes at least one Bronsted-Lowry acid, and wherein each ionic monomer independently includes at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or a combination thereof, wherein the solid- supported catalyst includes a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support, wherein each acidic moiety independently includes at least one Bronsted-Lowry acid, and wherein each ionic moiety independently includes at least one nitrogen-containing cationic group,
  • a method of producing one or more sugars from beer bottoms by: a) providing beer bottoms; b) contacting the beer bottoms with a catalyst to form a reaction mixture, wherein the catalyst is a polymeric catalyst or a solid-supported catalyst, wherein the polymeric catalyst includes acidic monomers and ionic monomers connected to form a polymeric backbone, wherein each acidic monomer independently includes at least one Bronsted-Lowry acid, and wherein each ionic monomer independently includes at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or a combination thereof, wherein the solid- supported catalyst includes a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support, wherein each acidic moiety independently includes at least one Bronsted-Lowry acid, and wherein each ionic moiety independently includes at least one nitrogen-containing cationic group, at least one phosphorous- containing cationic
  • a method of producing a food agent from biomass by: a) providing biomass; b) contacting the biomass with a catalyst to form a reaction mixture, wherein the catalyst is a polymeric catalyst or a solid-supported catalyst, wherein the polymeric catalyst includes acidic monomers and ionic monomers connected to form a polymeric backbone, wherein each acidic monomer independently includes at least one Bronsted-Lowry acid, and wherein each ionic monomer independently includes at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or a combination thereof, wherein the solid-supported catalyst includes a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support, wherein each acidic moiety independently includes at least one Bronsted-Lowry acid, and wherein each ionic moiety independently includes at least one nitrogen-containing cationic group, at least one phosphorous- containing cationic group, or a combination thereof;
  • step (b) further includes contacting the biomass and the catalyst with water to form a reaction mixture. In other embodiments, step (b) further includes contacting the biomass and the catalyst with a solvent to form a reaction mixture.
  • the method further includes pretreating the feedstock (e.g. , softwood, hardwood, cassava, bagasse, sugarbeet pulp, straw, paper sludge, oil palm, corn stover, food waste, enzymatic digestion residuals, beer bottoms, or other biomass, and any combination thereof) before contacting the feedstock with the catalyst to form the reaction mixture.
  • the feedstock e.g. , softwood, hardwood, cassava, bagasse, sugarbeet pulp, straw, paper sludge, oil palm, corn stover, food waste, enzymatic digestion residuals, beer bottoms, or other biomass, and any combination thereof
  • the pretreatment of the feedstock is selected from washing, solvent-extraction, solvent- swelling, comminution, milling, steam pretreatment, explosive steam pretreatment, dilute acid pretreatment, hot water pretreatment, alkaline pretreatment, lime pretreatment, wet oxidation, wet explosion, ammonia fiber explosion, organosolvent pretreatment, biological pretreatment, ammonia percolation, ultrasound, electroporation, microwave, supercritical C0 2 , supercritical H 2 0, ozone, and gamma irradiation, or any combination thereof.
  • the isolating of at least a portion of the liquid phase from the solid phase in step (d) produces a residual feedstock mixture
  • the method further includes: i) providing additional feedstock (e.g.
  • the additional feedstock (e.g. , softwood, hardwood, cassava, bagasse, sugarbeet pulp, straw, paper sludge, oil palm, corn stover, food waste, enzymatic digestion residuals, beer bottoms, and any combination thereof) in step (i) is the same type or a different type as the feedstock in step (a).
  • the one or more additional sugars produced in step (iii) is the same or a different type as the one or more sugars produced in step (c).
  • the method further includes contacting the additional feedstock and the residual feedstock mixture in step (iii) with additional catalyst, in which the additional catalyst can be any of the catalysts described herein (e.g. , a polymeric catalyst, a solid-supported catalyst, or a combination thereof).
  • the additional catalyst is the same or different as the catalyst in step (b).
  • the method further includes contacting the additional feedstock and the residual feedstock mixture with additional solvent.
  • the additional solvent is the same or different as the solvent in step (b).
  • the additional solvent includes water.
  • the method further includes recovering the catalyst after isolating at least a portion of the second liquid phase.
  • the catalyst described herein has one or more catalytic properties selected from: a) disruption of a hydrogen bond in cellulosic materials;
  • the catalyst has a greater specificity for cleavage of a glycosidic bond than dehydration of a monosaccharide in cellulosic materials.
  • a catalyst prepared according to any of the methods described above for degrading biomass into one or more monosaccharides, one or more oligosaccharides, or a combination thereof is also a use of a catalyst prepared according to any of the methods described above for degrading biomass into one or more monosaccharides, one or more oligosaccharides, or a combination thereof.
  • FIG. 1 illustrates a portion of an exemplary catalyst that has a polymeric backbone and side chains.
  • FIG. 2 illustrates a portion of an exemplary catalyst, in which a side chain with the acidic group is connected to the polymeric backbone by a linker and in which a side chain with the cationic group is connected directly to the polymeric backbone.
  • FIG. 3A illustrates a portion of an exemplary polymeric catalyst, in which the monomers are randomly arranged in an alternating sequence.
  • FIG. 3B illustrates a portion of an exemplary polymeric catalyst, in which the monomers are arranged in blocks of monomers, and the block of acidic monomers alternates with the block of ionic monomers.
  • FIGS. 4A and 4B illustrate a portion of exemplary polymeric catalysts with cross- linking within a given polymeric chain.
  • FIGS. 5A, 5B, 5C and 5D illustrate a portion of exemplary polymeric catalysts with cross-linking between two polymeric chains.
  • FIG. 6A illustrates a portion of an exemplary polymeric catalyst with a polyethylene backbone.
  • FIG. 6B illustrates a portion of an exemplary polymeric catalyst with a
  • FIG. 6C illustrates a portion of an exemplary polymeric catalyst with an ionomeric backbone.
  • FIG. 7A illustrates two side chains in an exemplary polymeric catalyst, in which there are three carbon atoms between the side chain with the Bronsted-Lowry acid and the side chain with the cationic group.
  • FIG. 7B illustrates two side chains in another exemplary polymeric catalyst, in which there are zero carbons between the side chain with the Bronsted-Lowry acid and the side chain with the cationic group.
  • FIG. 8A depicts an exemplary reaction to activate a carbon support by introducing a reactive linker by a Friedel-Crafts reaction
  • FIG. 8B depicts an exemplary reaction scheme to prepare a dual-functionalized catalyst from an activated carbon support, in which the catalyst has both acidic and ionic moieties.
  • catalysts including polymeric catalysts and solid-supported catalysts that can be used to hydrolyze cellulosic materials to produce monosaccharides, as well as oligosaccharides.
  • the catalysts can disrupt the hydrogen bond superstructure typically found in natural cellulosic materials, allowing the acidic pendant groups of the catalyst to come into chemical contact with the interior glycosidic bonds in the crystalline domains of cellulose.
  • the catalysts described herein provide effective cellulose digestion, as well as ease of recycle and reuse.
  • the ability to recycle and reuse the catalyst presents several advantages, including reducing the cost of converting lignocellulose into industrially important chemicals, such as sugars, oligosaccharides, organic acids, alcohols and aldehydes.
  • the catalysts described herein can penetrate deeply into the crystalline structure of cellulose, resulting in higher yields and faster kinetics for hydrolyzing cellulosic materials to produce monosaccharides and/or oligosaccharides.
  • the catalysts described herein are less corrosive, more easily handled, and can be easily recovered because they naturally phase separate from aqueous products. Further, the use of the catalysts provided herein does not require solubilization of the cellulosic material in a solvent such as molten metal halides, ionic liquids, or acid/organic solvent mixtures. Thus, provided herein are stable, recyclable, catalysts that can efficiently digest cellulosic materials on a commercially- viable scale.
  • Reference to "between” two values or parameters herein includes (and describes) embodiments that include those two values or parameters per se. For example, description referring to "between x and y” includes description of "x" and "y" per se.
  • “Bronsted-Lowry acid” refers to a molecule, or substituent thereof, in neutral or ionic form that is capable of donating a proton (hydrogen cation, H + ).
  • Homopolymer refers to a polymer having at least two monomer units, and where all the units contained within the polymer are derived from the same monomer.
  • One suitable example is polyethylene, where ethylene monomers are linked to form a uniform repeating chain (-CH 2 -CH 2 -CH 2 -).
  • Heteropolymer refers to a polymer having at least two monomer units, and where at least one monomeric unit differs from the other monomeric units in the polymer. Heteropolymer also refers to polymers having difunctionalized or trifunctionalized monomer units that can be incorporated in the polymer in different ways. The different monomer units in the polymer can be in a random order, in an alternating sequence of any length of a given monomer, or in blocks of monomers.
  • One suitable example is polyethyleneimidazolium, where if in an alternating sequence, would be the polymer depicted in FIG. 6C.
  • polystyrene- co-divinylbenzene where if in an alternating sequence, could be (-CH 2 -CH(phenyl)-CH 2 -CH(4- ethylenephenyl)-CH 2 -CH(phenyl)-CH 2 -CH(4-ethylenephenyl)-).
  • the ethenyl functionality could be at the 2, 3, or 4 position on the phenyl ring.
  • >/ w ⁇ denotes the attachment point of a moiety to the parent structure.
  • Ci_6 alkyl (which may also be referred to as 1-6C alkyl, C1-C6 alkyl, or Cl-6 alkyl) is intended to encompass, C 1; C 2 , C 3 , C 4 , C 5 , C 6 , C ⁇ , C1- 5 , C ⁇ , Q_
  • Ci-2 C2-6, C 2 _5, C2- , C 2 _ 3 , C 3 _6, C 3 _5, C 3 ⁇ , C4_6, C4_5, and C 5 _6 alkyl.
  • alkyl includes saturated straight-chained or branched monovalent hydrocarbon radicals, which contain only C and H when unsubstituted.
  • alkyl as used herein may have 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 1-3 alkyl).
  • Representative straight-chained alkyls include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl.
  • Representative branched alkyls 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.
  • alkyl residue having a specific number of carbons When an alkyl residue having a specific number of carbons is named, all geometric isomers having that number of carbons are intended to be encompassed and described; thus, for example, “butyl” is meant to include w-butyl, sec- butyl, iso-butyl, and iert-butyl; “propyl” includes w-propyl, and wo-propyl.
  • alkoxy refers to the group -O-alkyl, which is attached to the parent structure through an oxygen atom. Examples of alkoxy may include methoxy, ethoxy, propoxy, and isopropoxy. In some embodiments, alkoxy as used herein has 1 to 6 carbon atoms (e.g. , 0-(C 1-6 alkyl)), or 1 to 4 carbon atoms (e.g. , 0-(C 1-4 alkyl)).
  • alkenyl refers to straight-chained or branched monovalent hydrocarbon radicals, which contain only C and H when unsubstituted and at least one double bond.
  • 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).
  • alkenyl residue having a specific number of carbons is named, all geometric isomers having that number of carbons are intended to be encompassed and described; thus, for example, "butenyl” is meant to include w-butenyl, sec-butenyl, and wo-butenyl.
  • the one or more carbon-carbon double bonds can be internal (such as in 2-butenyl) or terminal (such as in 1-butenyl).
  • Examples of C 2 _ 4 alkenyl groups include ethenyl (C2), 1-propenyl (C3), 2- propenyl (C3), 1-butenyl (C4), 2-butenyl (C4), and butadienyl (C4).
  • C 2 _ 6 alkenyl groups include the aforementioned 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 octatrienyl (C8).
  • alkynyl refers to straight-chained or branched monovalent hydrocarbon radicals, which contain only C and H when unsubstituted and at least one triple bond.
  • alkynyl has 2 to 10 carbon atoms (e.g. , C 2 -io alkynyl), or 2 to 5 carbon atoms (e.g. , C 2 -5 alkynyl).
  • alkynyl residue having a specific number of carbons When an alkynyl residue having a specific number of carbons is named, all geometric isomers having that number of carbons are intended to be encompassed and described; thus, for example, "pentynyl” is meant to include w-pentynyl, sec-pentynyl, wo-pentynyl, and iert-pentynyl. Examples of alkynyl may include -C ⁇ CH or -C ⁇ C-CH 3 .
  • alkyl, alkoxy, alkenyl, and alkynyl at each occurrence may independently be unsubstituted or substituted by one or more of substituents.
  • substituted alkyl, substituted alkoxy, substituted alkenyl, and substituted alkynyl at each occurrence may independently have 1 to 5 substituents, 1 to 3 substituents, 1 to 2 substituents, or 1 substituent.
  • the one or more substituents of substituted alkyl, alkoxy, alkenyl, and alkynyl is independently selected from cycloalkyl, aryl, heteroalkyl (e.g.
  • each R a is independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl (e.g. , bonded through a ring carbon), -C(0)R' and -S(0) t R' (where t is 1 or 2), where each R' is independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl.
  • R a is independently hydrogen, alkyl, haloalkyl, cycloalkyl, aryl, aralkyl (e.g. , alkyl substituted with aryl, bonded to parent structure through the alkyl group),
  • heterocycloalkyl or heteroaryl.
  • Heteroalkyl includes alkyl, alkenyl and alkynyl groups, respectively, wherein one or more skeletal chain atoms are selected from an atom other than carbon, e.g., oxygen, nitrogen, sulfur, phosphorus, or any combinations thereof.
  • heteroalkyl may be an ether where at least one of the carbon atoms in the alkyl group is replaced with an oxygen atom.
  • a numerical range can be given, e.g., C 1-4 heteroalkyl which refers to the chain length in total, which in this example is 4 atoms long.
  • heteroalkyl which includes the heteroatom center in the atom chain length description. Connection to the rest of the parent structure can be through, in one embodiment, a heteroatom, or, in another embodiment, a carbon atom in the heteroalkyl chain.
  • Heteroalkyl groups may include, for example, ethers such as methoxyethanyl (- CH 2 CH 2 OCH 3 ), ethoxymethanyl (-CH 2 OCH 2 CH 3 ), (methoxymethoxy)ethanyl (-
  • heteroalkyl, heteroalkenyl, or heteroalkynyl may be unsubstituted or substituted by one or more of substituents.
  • heteroalkynyl may have 1 to 5 substituents, 1 to 3 substituents, 1 to 2 substituents, or 1 substituent.
  • Examples for heteroalkyl, heteroalkenyl, or heteroalkynyl substituents may include the substituents described above for alkyl.
  • Carbocyclyl may 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).
  • the cycloalkyl, cycloalkenyl, or cycloalkynyl can consist of one ring, such as cyclohexyl, or multiple rings, such as adamantyl.
  • a cycloalkyl, cycloalkenyl, or cycloalkynyl with more than one ring can be fused, spiro or bridged, or combinations thereof.
  • cycloalkyl, cycloalkenyl, and cycloalkynyl has 3 to 10 ring atoms (i.e., C 3 -Cio cycloalkyl, C 3 -Cio 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.
  • cycloalkyl, cycloalkenyl, or cycloalkynyl includes bridged and spiro-fused cyclic structures containing no heteroatoms.
  • cycloalkyl, cycloalkenyl, or cycloalkynyl includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of ring atoms) groups.
  • C 3 _ 6 carbocyclyl groups 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 carbocyclyl groups may include, for example, the aforementioned C 3 _ 6 carbocyclyl groups as well as cycloheptyl (C 7 ), cycloheptadienyl (C 7 ), cycloheptatrienyl (C 7 ), cyclooctyl (C 8 ), bicyclo[2.2.1]heptanyl, and bicyclo[2.2.2]octanyl.
  • C 3 _io carbocyclyl groups may include, for example, the aforementioned C 3 _ 8 carbocyclyl groups as well as octahydro-lH-indenyl, decahydronaphthalenyl, and spiro [4.5 ] decanyl .
  • Heterocyclyl refers to carbocyclyl as described above, with one or more ring heteroatoms independently selected from nitrogen, oxygen, phosphorous, and sulfur.
  • Heterocyclyl may include, for example, heterocycloalkyl, heterocycloalkenyl, and heterocycloalknyl.
  • heterocyclyl is a 3- to 18-membered non-aromatic monocyclic or polycyclic moiety that has at least one heteroatom selected from nitrogen, oxygen, phosphorous and sulfur.
  • the heterocyclyl can be a monocyclic or polycyclic (e.g. , bicyclic, tricyclic or tetracyclic), wherein polycyclic ring systems can be a fused, bridged or spiro ring system.
  • Heterocyclyl polycyclic ring systems can include one or more heteroatoms in one or both rings.
  • An N-containing heterocyclyl moiety refers to an non-aromatic group in which at least one of the skeletal atoms of the ring is a nitrogen atom.
  • heterocyclyl group is optionally oxidized.
  • One or more nitrogen atoms, if present, are optionally quaternized.
  • heterocyclyl may also include ring systems substituted with one or more oxide (-0-) substituents, such as piperidinyl N-oxides.
  • the heterocyclyl is attached to the parent molecular structure through any atom of the ring(s).
  • heterocyclyl also includes ring systems with one or more fused carbocyclyl, aryl or heteroaryl groups, wherein the point of attachment is either on the carbocyclyl or heterocyclyl ring.
  • heterocyclyl is a 5-10 membered non- aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen and sulfur (e.g. , 5-10 membered heterocyclyl).
  • a heterocyclyl group is a 5-8 membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen and sulfur (e.g. , 5-8 membered heterocyclyl).
  • a heterocyclyl group is a 5-6 membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen and sulfur (e.g. , 5-6 membered heterocyclyl).
  • the 5-6 membered heterocyclyl has 1-3 ring heteroatoms selected from nitrogen, oxygen and sulfur.
  • the 5-6 membered heterocyclyl has 1-2 ring heteroatoms selected from nitrogen, oxygen and sulfur.
  • the 5-6 membered heterocyclyl has 1 ring heteroatom selected from nitrogen, oxygen and sulfur.
  • Exemplary 3-membered heterocyclyls containing 1 heteroatom may include azirdinyl, oxiranyl, thiorenyl.
  • Exemplary 4-membered heterocyclyls containing 1 heteroatom may include azetidinyl, oxetanyl and thietanyl.
  • Exemplary 5-membered heterocyclyls containing 1 heteroatom may include tetrahydrofuranyl, dihydrofuranyl, tetrahydrothiophenyl,
  • Exemplary 5- membered heterocyclyls containing 2 heteroatoms may include dioxolanyl, oxathiolanyl and dithiolanyl.
  • Exemplary 5-membered heterocyclyls containing 3 heteroatoms may include triazolinyl, oxadiazolinyl, and thiadiazolinyl.
  • Exemplary 6-membered heterocyclyl groups containing 1 heteroatom may include piperidinyl, tetrahydropyranyl, dihydropyridinyl, and thianyl.
  • Exemplary 6-membered heterocyclyl groups containing 2 heteroatoms may include piperazinyl, morpholinyl, dithianyl, dioxanyl. Exemplary 6-membered heterocyclyl groups containing 2 heteroatoms may include triazinanyl. Exemplary 7-membered heterocyclyl groups containing 1 heteroatom may include azepanyl, oxepanyl and thiepanyl. Exemplary 8-membered heterocyclyl groups containing 1 heteroatom may include azocanyl, oxecanyl and thiocanyl. Exemplary bicyclic heterocyclyl groups may include indolinyl, isoindolinyl,
  • 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).
  • aryl as used herein has 6 to 10 ring atoms (e.g., C 6 -C 10 aromatic or C 6 -C 10 aryl) which has at least one ring having a conjugated pi electron system.
  • ring atoms e.g., C 6 -C 10 aromatic or C 6 -C 10 aryl
  • bivalent radicals formed from substituted benzene derivatives and having the free valences at ring atoms are named as substituted phenylene radicals.
  • aryl may have more than one ring where at least one ring is non-aromatic can be connected to the parent structure at either an aromatic ring position or at a non-aromatic ring position.
  • aryl includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of ring atoms) groups.
  • Heteroaryl refers to an aromatic group having a single ring, multiple rings, or multiple fused rings, with one or more ring heteroatoms independently selected from nitrogen, oxygen, phosphorous, and sulfur.
  • 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.
  • 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 a cyclic array) having ring carbon atoms and 1 to 6 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, phosphorous and sulfur (e.g. , 5- 18 membered heteroaryl).
  • heteroaryl may have a single ring (e.g. , pyridyl, pyridinyl, imidazolyl) or multiple condensed rings (e.g.
  • heteroaryl may have more than one ring where at least one ring is non-aromatic can be connected to the parent structure at either an aromatic ring position or at a non-aromatic ring position. In one embodiment, heteroaryl may have more than one ring where at least one ring is non-aromatic is connected to the parent structure at an aromatic ring position.
  • Heteroaryl polycyclic ring systems can include one or more heteroatoms in one or both rings.
  • an N-containing “heteroaryl” refers to an aromatic group in which at least one of the skeletal atoms of the ring is a nitrogen atom.
  • One or more heteroatom(s) in the heteroaryl group can be optionally oxidized.
  • One or more nitrogen atoms, if present, are optionally quaternized.
  • heteroaryl may include ring systems substituted with one or more oxide (-0-) substituents, such as pyridinyl N-oxides. The heteroaryl may be attached to the parent molecular structure through any atom of the ring(s).
  • heteroaryl may include ring systems with one or more fused aryl groups, wherein the point of attachment is either on the aryl or on the heteroaryl ring.
  • heteroaryl may include ring systems with one or more carbocycyl or heterocycyl groups wherein the point of attachment is on the heteroaryl ring.
  • a heteroaryl group is a 5- 10 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, phosphorous, and sulfur (e.g. , 5- 10 membered heteroaryl).
  • a heteroaryl group is a 5-8 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, phosphorous, and sulfur (e.g. , 5-8 membered heteroaryl).
  • a heteroaryl group is a 5-6 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, phosphorous, and sulfur (e.g. , 5-6 membered heteroaryl).
  • the 5-6 membered heteroaryl has 1-3 ring heteroatoms selected from nitrogen, oxygen, phosphorous, and sulfur. In some embodiments, the 5-6 membered heteroaryl has 1-2 ring heteroatoms selected from nitrogen, oxygen, phosphorous, and sulfur. In some embodiments, the 5-6 membered heteroaryl has 1 ring heteroatom selected from nitrogen, oxygen, phosphorous, and sulfur.
  • heteroaryls may include azepinyl, acridinyl, benzimidazolyl,
  • benzothiadiazolyl benzo[b][l,4]dioxepinyl, benzo[b][l,4]oxazinyl, 1,4-benzodioxanyl, benzonaphthofuranyl, benzoxazolyl, benzodioxolyl, benzodioxinyl, benzoxazolyl, benzopyranyl, benzopyranonyl, benzofuranyl, benzofuranonyl, benzofurazanyl, benzothiazolyl, benzothienyl (benzothiophenyl), benzothieno[3,2-d]pyrimidinyl, benzotriazolyl,
  • carbocyclyl including, for example, cycloalkyl, cycloalkenyl or cycloalkynyl
  • aryl, heteroaryl, and heterocyclyl at each occurrence may independently be unsubstituted or substituted by one or more of substituents.
  • a substituted carbocyclyl including, for example, substituted cycloalkyl, substituted cycloalkenyl or substituted cycloalkynyl
  • substituted aryl, substituted heteroaryl, substituted heterocyclyl at each occurrence may be independently may independently have 1 to 5 substituents, 1 to 3 substituents, 1 to 2 substituents, or 1 substituent.
  • carbocyclyl including, for example, cycloalkyl, cycloalkenyl or cycloalkynyl
  • aryl, heteroaryl, heterocyclyl substituents may include alkyl alkenyl, alkoxy, cycloalkyl, aryl, heteroalkyl (e.g.
  • any moiety referred to as a "linker” refers to the moiety has having bivalency.
  • “alkyl linker” refers to the same residues as alkyl, but having bivalency. Examples of alkyl linkers
  • Alkynyl linker refers to the same residues as alkynyl, but having bivalency.
  • alkynyl linkers include -C ⁇ C- or -C ⁇ C-CH 2 -
  • “carbocyclyl linker”, aryl linker”, “heteroaryl linker”, and “heterocyclyl linker” refer to the same residues as carbocyclyl, aryl, heteroaryl, and heterocyclyl, respectively, but having bivalency.
  • Amino refers to -N(R a )(R b ), where each R a and R is independently selected from hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl (e.g. , bonded through a chain carbon), cycloalkyl, aryl, heterocycloalkyl (e.g. , bonded through a ring carbon), heteroaryl (e.g.
  • amino includes amido (e.g. , -NR a C(0)R b ).
  • the alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl moiety of R a and R b may be further substituted as described herein.
  • R a and R b may be the same or different.
  • amino is -NH 2 (where R a and R b are each hydrogen).
  • R a and R b are other than hydrogen
  • R a and R b can be combined with the nitrogen atom to which they are attached to form a 3-, 4-, 5-, 6-, or 7- membered ring.
  • Such examples may include 1-pyrrolidinyl and 4-morpholinyl.
  • Ammonium refers to -N(R a )(R b )(R c ) + , where each R a , R and R c is independently selected from hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl (e.g. , bonded through a chain carbon), cycloalkyl, aryl, heterocycloalkyl (e.g. , bonded through a ring carbon), heteroaryl (e.g.
  • R' is independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl; or any two of R a , R b and R c may be taken together with the atom to which they are attached to form a cycloalkyl, heterocycloalkyl; or any three of R a , R b and R c may be taken together with the atom to which they are attached to form aryl or heteroaryl.
  • the alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl moiety of any one or more of R a , R b and R c may be further substituted as described herein.
  • R a , R b and R c may be the same or different.
  • amino also refers to N-oxides of the groups -N + (H)(R a )0 " , and -N + (R a )(R b )0-, where R a and R b are as described herein, where the N-oxide is bonded to the parent structure through the N atom.
  • N-oxides can be prepared by treatment of the
  • Amide refers to a chemical moiety with formula -C(O) N(R a )(R b ) or - NR a C(0)R b , where R a and R b at each occurrence are as described herein.
  • amido is a C 1-4 amido, which includes the amide carbonyl in the total number of carbons in the group.
  • Carbonyl refers to -C(0)R a , where R a is hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, heteroaryl, -N(R') 2> -S(0) t R' , where each R' is independently hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl, and t is 1 or 2.
  • each R' are other than hydrogen
  • the two R' moieties can be combined with the nitrogen atom to which they are attached to form a 3-, 4-, 5-, 6-, or 7-membered ring.
  • carbonyl includes amido (e.g. , -C(O) N(R a )(R b )).
  • “Cyano” refers to a -CN group.
  • Halo means fluoro, chloro, bromo or iodo.
  • haloalkyl means alkyl, alkenyl, alkynyl and alkoxy moieties as described above, wherein one or more hydrogen atoms are replaced by halo.
  • a residue is substituted with more than one halo groups, it may be referred to by using a prefix corresponding to the number of halo groups attached.
  • dihaloaryl, dihaloalkyl, and trihaloaryl refer to aryl and alkyl substituted with two ("di") or three ("tri") halo groups, which may be, but are not necessarily, the same halogen; thus, for example, 3,5-difluorophenyl, 3 -chloro-5 -fluorophenyl, 4-chloro-3 -fluorophenyl, and 3,5- difluoro-4-chlorophenyl is within the scope of dihaloaryl.
  • a haloalkyl group include difluoromethyl (-CHF 2 ), trifluoromethyl (-CF 3 ), 2,2,2-trifluoroethyl, and
  • Perhaloalkyl refers to an alkyl or alkylene group in which all of the hydrogen atoms have been replaced with a halogen (e.g. , fluoro, chloro, bromo, or iodo). In some embodiments, all of the hydrogen atoms are each replaced with fluoro. In some embodiments, all of the hydrogen atoms are each replaced with chloro. Examples of perhaloalkyl groups include -CF 3 , - CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CC1 3 , -CFC1 2 , and -CF 2 C1.
  • Thio refers to -SR a , wherein R a is as described herein.
  • Thiol refers to the group - R a SH, wherein R a is as described herein.
  • Sulfinyl refers to -S(0)R a . In some embodiments, sulfinyl is -S(0)N(R a )(R b ). “Sulfonyl” refers to the -S(0 2 )R a . In some embodiments, sulfonyl is -S(0 2 ) N(R a )(R b ) or - S(0 2 )OH. For each of these moieties, it should be understood that R a and R b are as described herein.
  • Moiety refers to a specific segment or functional group of a molecule. Chemical moieties are often recognized chemical entities embedded in or appended to a molecule.
  • the term "unsubstituted” means that for carbon atoms, only hydrogen atoms are present besides those valencies linking the atom to the parent molecular group.
  • One example is propyl (-CH 2 -CH 2 -CH 3 ).
  • valencies not linking the atom to the parent molecular group are either hydrogen or an electron pair.
  • sulfur atoms valencies not linking the atom to the parent molecular group are either hydrogen, oxygen or electron pair(s).
  • substituted or “substitution” means that at least one hydrogen present on a group (e.g.
  • a carbon or nitrogen atom is replaced with a permissible substituent, e.g. , a substituent which upon substitution for the hydrogen results in a stable compound, e.g., a compound which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, or other reaction.
  • a permissible substituent e.g., a substituent which upon substitution for the hydrogen results in a stable compound, e.g., a compound which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, or other reaction.
  • substituted group can have a substituent at one or more substitutable positions of the group, and when more than one position in any given structure is substituted, the substituent is either the same or different at each position.
  • Substituents include one or more group(s) individually and independently selected from alkyl alkenyl, alkoxy, cycloalkyl, aryl, heteroalkyl (e.g.
  • substituent groups are specified by their conventional chemical formulae, written from left to right, they equally encompass the chemically identical substituents that would result from writing the structure from right to left, e.g., -CH 2 0- is equivalent to -OCH 2 -.
  • the catalysts described herein may include polymeric catalysts and solid-supported catalysts.
  • the catalyst is a polymer made up of acidic monomers and ionic monomers (which are also referred to herein as "ionomers") connected to form a polymeric backbone.
  • Each acidic monomer includes at least one Bronsted-Lowry acid
  • each ionic monomer includes at least one nitrogen-containing cationic group, at least one phosphorous- containing cationic group, or any combination thereof.
  • at least some of the acidic and ionic monomers may independently include a linker connecting the Bronsted-Lowry acid or the cationic group (as applicable) to a portion of the polymeric backbone.
  • the Bronsted-Lowry acid and the linker together form a side chain.
  • the cationic group and the linker together form a side chain.
  • the side chains are pendant from the polymeric backbone.
  • the catalyst is solid-supported, having acidic moieties and ionic moieties each attached to a solid support.
  • Each acidic moiety independently includes at least one Bronsted-Lowry acid
  • each ionic moiety includes at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or any combination thereof.
  • at least some of the acidic and ionic moieties may independently include a linker connecting the Bronsted-Lowry acid or the cationic group (as applicable) to the solid support.
  • catalyst 808 is an exemplary solid-supported catalyst with acidic and ionic moieties.
  • the polymeric catalysts include a plurality of acidic monomers, where as the solid-supported catalysts includes a plurality of acidic moieties attached to a solid support.
  • a plurality of acidic monomers (e.g. , of a polymeric catalyst) or a plurality of acidic moieties (e.g. , of a solid-supported catalyst) has at least one Bronsted- Lowry acid.
  • a plurality of acidic monomers (e.g. , of a polymeric catalyst) or a plurality of acidic moieties (e.g. , of a solid- supported catalyst) has one Bronsted- Lowry acid or two Bronsted-Lowry acids.
  • a plurality of the acidic monomers (e.g. , of a polymeric catalyst) or a plurality of the acidic moieties (e.g. , of a solid- supported catalyst) has one Bronsted-Lowry acid, while others have two Bronsted-Lowry acids.
  • each Bronsted-Lowry acids is independently selected from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, and boronic acid. In certain embodiments, each Bronsted-Lowry acids is independently sulfonic acid or phosphonic acid. In one embodiment, each Bronsted-Lowry acid is sulfonic acid. It should be understood that the Bronsted-Lowry acids in an acidic monomer (e.g. , of a polymeric catalyst) or an acidic moiety (e.g. , of a solid-supported catalyst) may be the same at each occurrence or different at one or more occurrences.
  • an acidic monomer e.g. , of a polymeric catalyst
  • an acidic moiety e.g. , of a solid-supported catalyst
  • one or more of the acidic monomers of a polymeric catalyst are directly connected to the polymeric backbone, or one or more of the acidic moieties of a solid-supported catalyst are directly connected to the solid support.
  • one or more of the acidic monomers (e.g. , of a polymeric catalyst) or one or more acidic moieties (e.g. , of a solid-supported catalyst) each independently further includes a linker connecting the Bronsted-Lowry acid to the polymeric backbone or the solid support (as the case may be).
  • some of the Bronsted-Lowry acids are directly connected to the polymeric backbone or the solid support (as the case may be), while other the Bronsted-Lowry acids are connected to the polymeric backbone or the solid support (as the case may be) by a linker.
  • each linker is independently selected from unsubstituted or substituted alkyl linker, unsubstituted or substituted cycloalkyl linker, unsubstituted or substituted alkenyl linker, unsubstituted or substituted aryl linker, and unsubstituted or substituted heteroaryl linker.
  • the linker is unsubstituted or substituted aryl linker, or unsubstituted or substituted heteroaryl linker.
  • the linker is 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.
  • each linker in an acidic monomer (e.g. , of a polymeric catalyst) or an acidic moiety (e.g. , of a solid-supported catalyst) is independently selected from: unsubstituted alkyl linker; alkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted cycloalkyl linker; cycloalkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted alkenyl linker; alkenyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted aryl linker; aryl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted heteroaryl linker; or heteroaryl linker substituted 1
  • the acidic monomers e.g. , of a polymeric catalyst
  • one or more acidic moieties e.g. , of a solid-supported catalyst
  • linker may have the same linker, or independently have different linkers.
  • each acidic monomer e.g. , of a polymeric catalyst
  • each acidic moiety e.g. , of a solid-supported catalyst
  • each Z is independently C(R 2 )(R 3 ), N(R 4 ), S, S(R 5 )(R 6 ), S(0)(R 5 )(R 6 ), S0 2 , or O, wherein any two adjacent Z can (to the extent chemically feasible) be joined by a double bond, or taken together to form cycloalkyl, heterocycloalkyl, aryl or heteroaryl; each m is independently selected from 0, 1, 2, and 3; each n is independently selected from 0, 1, 2, and 3; each R 2 , R 3 , and R 4 is independently hydrogen, alkyl, heteroalkyl, cycloalkyl, heterocyclyl, aryl, or heteroaryl; and each R 5 and R 6 is independently alkyl, heteroalkyl, cycloalkyl, heterocyclyl, aryl, or heteroaryl.
  • each acidic monomer e.g. , of a polymeric catalyst
  • each acidic moiety e.g. , of a polymeric
  • each acidic monomer e.g. , of a polymeric catalyst
  • each acidic moiety e.g. , of a solid-supported catalyst
  • each acidic monomer e.g. , of a polymeric catalyst
  • each acidic moiety e.g. , of a solid-supported catalyst
  • each acidic monomer e.g. , of a polymeric catalyst
  • each acidic moiety e.g. , of a solid-supported catalyst
  • each acidic monomer e.g. , of a polymeric catalyst
  • each acidic moiety e.g. , of a solid-supported catalyst
  • each acidic monomer e.g. , of a polymeric catalyst
  • each acidic moiety e.g. , of a solid-supported catalyst
  • Z can be chosen from C(R 2 )(R 3 ), N(R 4 ), S0 2 , and O.
  • any two adjacent Z can be taken together to form a group selected from a heterocycloalkyl, aryl, and heteroaryl.
  • any two adjacent Z can be joined by a double bond. Any combination of these embodiments is also contemplated (as chemically feasible).
  • m is 2 or 3. In other embodiments, n is 1, 2, or 3.
  • R 1 can be hydrogen, alkyl or heteroalkyl. In some embodiments, R 1 can be
  • each R , R , and R can independently be
  • each R , R and R can independently be heteroalkyl, cycloalkyl, heterocyclyl, or heteroaryl.
  • each R 5 and R 6 can independently be alkyl, heterocyclyl, aryl, or heteroaryl.
  • any two adjacent Z can be taken together to form cycloalkyl, heterocycloalkyl, aryl or heteroaryl.
  • the polymeric catalysts and solid-supported catalysts described herein contain monomers or moieties, respectively, that have 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.
  • the acidic monomers of the polymeric catalyst may have a side chain with a Bronsted-Lowry acid that is connected to the polymeric backbone by a linker.
  • the acidic moieties of the solid-supported catalyst may have a Bronsted- Lowry acid that is attached to the solid support by a linker.
  • Side chains (e.g. , of a polymeric catalyst) or acidic moieties (e.g. , of a solid-supported catalyst) with one or more Bronsted-Lowry acids connected by a linker can include, for example,
  • L is an unsubstituted alkyl linker, alkyl linker substituted with oxo, unsubstituted cycloalkyl, unsubstituted aryl, unsubstituted heterocycloalkyl, and unsubstituted heteroaryl; and r is an integer.
  • L is an alkyl linker. In other embodiments L is methyl, ethyl, propyl, butyl. In yet other embodiments, the linker is ethanoyl, propanoyl, benzoyl. In certain embodiments, r is 1, 2, 3, 4, or 5 (as applicable or chemically feasible).
  • At least some of the acidic side chains (e.g. , of a polymeric catalyst) and at least some of the acidic moieties (e.g. , of a solid-supported catalyst) may be:
  • s is 1 to 9, or 1 to 8, or 1 to 7, or 1 to 6, or 1 to 5, or 1 to 4, or 1 to 3, or 2, or 1.
  • w is 0 to 9, or 0 to 8, or 0 to 7, or 0 to 6, or 0 to 5, or 0 to 4, or 0 to 3, or 0 to 2, 1 or 0).
  • At least some of the acidic side chains (e.g. , of a polymeric catalyst) and at least some of the acidic moieties (e.g. , of a solid-supported catalyst) may be:
  • At least some of the acidic side chains (e.g. , of a polymeric catalyst) and at least some of the acidic moieties (e.g. , of a solid-supported catalyst) may be:
  • At least some of the acidic side chains (e.g. , of a polymeric catalyst) and at least some of the acidic moieties (e.g. , of a solid-supported catalyst) may be:
  • At least some of the acidic side chains (e.g. , of a polymeric catalyst) and at least some of the acidic moieties (e.g. , of a solid-supported catalyst) may be:
  • the acidic monomers e.g. , of a polymeric catalyst
  • the acidic moieties e.g. , of a solid-supported catalyst
  • Side chains directly connect to the polymeric backbone (e.g. , of a polymeric catalyst) or acidic moieties (e.g. , of a solid- supported catalyst) directly attached to the solid support may can include, for example,
  • the polymeric catalysts include a plurality of ionic monomers, where as the solid-supported catalysts includes a plurality of ionic moieties attached to a solid support.
  • a plurality of ionic monomers e.g. , of a polymeric catalyst
  • a plurality of ionic moieties e.g. , of a solid- supported catalyst
  • a plurality of ionic monomers e.g. , of a polymeric catalyst
  • a plurality of ionic moieties e.g. , of a solid- supported catalyst
  • a plurality of ionic monomers e.g.
  • a plurality of ionic monomers e.g. , of a polymeric catalyst
  • a plurality of ionic moieties e.g. , of a solid-supported catalyst
  • a plurality of ionic monomers e.g. , of a polymeric catalyst
  • a plurality of ionic moieties e.g. , of a solid-supported catalyst
  • the ionic monomers e.g. , of a polymeric catalyst
  • ionic moieties e.g. , of a solid-supported catalyst
  • the cationic groups can be the same or different.
  • each ionic monomer (e.g. , of a polymeric catalyst) or each ionic moiety (e.g. , of a solid-supported catalyst) is a nitrogen-containing cationic group.
  • each ionic monomer (e.g. , of a polymeric catalyst) or each ionic moiety (e.g. , of a solid-supported catalyst) is a phosphorous-containing cationic group.
  • each cationic group in the polymeric catalyst or solid-supported catalyst is imidazolium.
  • the cationic group in some monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid-supported catalyst) is imidazolium, while the cationic group in other monomers (e.g.
  • each cationic group in the polymeric catalyst or solid-supported catalyst is a substituted phosphonium.
  • the cationic group in some monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid-supported catalyst) is triphenyl phosphonium, while the cationic group in other monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid- supported catalyst) is imidazolium.
  • the nitrogen-containing cationic group at each occurrence can be independently selected from pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyradizimium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.
  • the nitrogen-containing cationic group at each occurrence can be independently selected from imidazolium, pyridinium, pyrimidinium, morpholinium, piperidinium, and piperizinium.
  • the nitrogen-containing cationic group can be imidazolium.
  • the phosphorous-containing cationic group at each occurrence can be independently selected from triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.
  • the phosphorous-containing cationic group at each occurrence can be independently selected from triphenyl phosphonium, trimethyl phosphonium, and triethyl phosphonium.
  • the phosphorous-containing cationic group can be triphenyl phosphonium.
  • one or more of the ionic monomers of a polymeric catalyst are directly connected to the polymeric backbone, or one or more of the ionic moieties of a solid- supported catalyst are directly connected to the solid support.
  • one or more of the ionic monomers (e.g. , of a polymeric catalyst) or one or more ionic moieties (e.g. , of a solid- supported catalyst) each independently further includes a linker connecting the cationic group to the polymeric backbone or the solid support (as the case may be).
  • some of the cationic groups are directly connected to the polymeric backbone or the solid support (as the case may be), while other the cationic groups are connected to the polymeric backbone or the solid support (as the case may be) by a linker.
  • each linker is independently selected from unsubstituted or substituted alkyl linker, unsubstituted or substituted cycloalkyl linker, unsubstituted or substituted alkenyl linker, unsubstituted or substituted aryl linker, and unsubstituted or substituted heteroaryl linker.
  • the linker is unsubstituted or substituted aryl linker, or unsubstituted or substituted heteroaryl linker.
  • the linker is 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.
  • each linker in an ionic monomer (e.g. , of a polymeric catalyst) or an ionic moiety (e.g. , of a solid-supported catalyst) is independently selected from: unsubstituted alkyl linker; alkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted cycloalkyl linker; cycloalkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted alkenyl linker; alkenyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted aryl linker; aryl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted heteroaryl linker; or heteroaryl linker substitute
  • ionic monomers e.g. , of a polymeric catalyst
  • one or more ionic moieties e.g. , of a solid-supported catalyst
  • linker may have the same linker, or independently have different linkers.
  • each ionic monomer e.g. , of a polymeric catalyst
  • each ionic moiety e.g. , of a solid-supported catalyst
  • each Z is independently C(R 2 )(R 3 ), N(R 4 ), S, S(R 5 )(R 6 ), S(0)(R 5 )(R 6 ), S0 2 , or O, wherein any two adjacent Z can (to the extent chemically feasible) be joined by a double bond, or taken together to form cycloalkyl, heterocycloalkyl, aryl or heteroaryl; each X is independently F, CI " , Br “ , ⁇ , N0 2 " , N0 3 , S0 4 2” , R 7 S0 4 " , R 7 C0 2 " , P0 4 2” , R 7 P0 3 ,
  • R P0 2 " where S0 4 " and P0 4 " are each independently associated with at least two cationic groups at any X position on any ionic monomer, and each m is independently 0, 1, 2, or 3; each n is independently 0, 1, 2, or 3; each R 1 , R 2 , R 3 and R 4 is independently hydrogen, alkyl, heteroalkyl, cycloalkyl, heterocyclyl, aryl, or heteroaryl; each R 5 and R 6 is independently alkyl, heteroalkyl, cycloalkyl, heterocyclyl, aryl, or heteroaryl; and each R is independently hydrogen, C 1-4 alkyl, or Ci ⁇ heteroalkyl.
  • Z can be chosen from C(R 2 )(R 3 ), N(R 4 ), S0 2 , and O.
  • any two adjacent Z can be taken together to form a group selected from a heterocycloalkyl, aryl and heteroaryl.
  • any two adjacent Z can be joined by a double bond.
  • each X can be CI " , N0 3 " , S0 4 2- " , R 7 S0 4 - " , or R 7 C0 2 - " , where R can be hydrogen or Ci ⁇ alkyl.
  • each X can be CI “ , Br “ , ⁇ , HS0 4 " , HC0 2 “ , CH C0 2 “ , or N0 3 " .
  • X is acetate.
  • X is bisulfate.
  • X is chloride.
  • X is nitrate.
  • m is 2 or 3. In other embodiments, n is 1, 2, or 3. In some embodiments, each R 2 , R 3 , and R 4 can be independently hydrogen, alkyl, heterocyclyl, aryl, or 2 3 4
  • each R , R and R can be independently heteroalkyl, cycloalkyl, heterocyclyl, or heteroaryl.
  • each R 5 and R 6 can be independently alkyl, heterocyclyl, aryl, or heteroaryl.
  • any two adjacent Z can be taken together to form cycloalkyl, heterocycloalkyl, aryl or heteroaryl.
  • the ionic monomers of the polymeric catalyst may have a side chain with a cationic group that is connected to the polymeric backbone by a linker.
  • the ionic moieties of the solid-supported catalyst may have a cationic group that is attached to the solid support by a linker.
  • Side chains (e.g. , of a polymeric catalyst) or ionic moieties (e.g. , of a solid-supported catalyst) with one or more cationic groups connected by a linker can include, for example,
  • L is an unsubstituted alkyl linker, alkyl linker substituted with oxo, unsubstituted cycloalkyl, unsubstituted aryl, unsubstituted heterocycloalkyl, and unsubstituted heteroaryl; each R la , R lb and R lc are independently hydrogen or alkyl; or R la and R lb are taken together with the nitrogen atom to which they are attached to form an unsubstituted
  • R la and R lb are taken together with the nitrogen atom to which they are attached to form an unsubstituted heteroaryl or substituted heteroaryl, and R lc is absent; r is an integer; and
  • X is as described above for Formulas VIIA-XIB.
  • L is methyl, ethyl, propyl, butyl.
  • the linker is ethanoyl, propanoyl, benzoyl.
  • r is 1, 2, 3, 4, or 5 (as applicable or chemically feasible).
  • each linker is independently selected from: unsubstituted alkyl linker; alkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted cycloalkyl linker; cycloalkyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted alkenyl linker; alkenyl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted aryl linker; aryl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino; unsubstituted heteroaryl linker; or heteroaryl linker substituted 1 to 5 substituents independently selected from oxo, hydroxy, halo, amino.
  • each linker is an unsubstituted alkyl linker or an alkyl linker with an oxo substituent.
  • r is 1, 2, 3, 4, or 5 (as applicable or chemically feasible).
  • At least some of the ionic side chains (e.g. , of a polymeric catalyst) and at least some of the ionic moieties (e.g. , of a solid-supported catalyst) may be:
  • each R la , R lb and R lc are independently hydrogen or alkyl; or R la and R lb are taken together with the nitrogen atom to which they are attached to form an unsubstituted
  • R la and R lb are taken together with the nitrogen atom to which they are attached to form an unsubstituted heteroaryl or substituted heteroaryl, and R lc is absent; s is an integer; v is 0 to 10; and
  • X is as described above for Formulas VIIA-XIB.
  • s is 1 to 9, or 1 to 8, or 1 to 7, or 1 to 6, or 1 to 5, or 1 to 4, or 1 to 3, or 2, or 1.
  • v is 0 to 9, or 0 to 8, or 0 to 7, or 0 to 6, or 0 to 5, or 0 to 4, or 0 to 3, or 0 to 2, 1 or 0).
  • At least some of the ionic side chains (e.g. , of a polymeric catalyst) and at least some of the ionic moieties (e.g. , of a solid-supported catalyst) may be:
  • the nitrogen-containing side chain e.g. , of a polymeric catalyst
  • moiety e.g. , of a solid-supported catalyst
  • the nitrogen-containing side chain e.g. , of a polymeric catalyst
  • moiety e.g. , of a solid-supported catalyst
  • the nitrogen-containing side chain e.g. , of a polymeric catalyst
  • moiety e.g. , of a solid-supported catalyst
  • the nitrogen-containing side chain e.g. , of a polymeric catalyst
  • moiety e.g. , of a solid-supported catalyst
  • the nitrogen-containing side chain e.g. , of a polymeric catalyst
  • moiety e.g. , of a solid-supported catalyst
  • the nitrogen-containing side chain e.g. , of a polymeric catalyst
  • moiety e.g. , of a solid-supported catalyst
  • the ionic monomers e.g. , of a polymeric catalyst
  • the ionic monomers can have a side chain with a cationic group that is directly connected to the polymeric backbone.
  • the ionic moieties e.g. , of a solid-supported catalyst
  • Side chains e.g. , of a polymeric catalyst directly connect to the polymeric backbone or ionic moieties (e.g. , of a solid-supported catalyst) directly attached to the solid support may can include, for example,
  • such nitrogen-containing side chains e.g., of a polymeric catalyst
  • moieties e.g., of a solid-supported catalyst
  • the nitrogen-containing cationic group can be an N-oxide, where the negatively charged oxide (0-) is not readily dissociable from the nitrogen cation.
  • Non- limiting examples of such groups include, for example,
  • the phosphorous-containing side chain e.g. , of a polymeric catalyst
  • moiety e.g. , of a solid-supported catalyst
  • the phosphorous-containing side chain e.g. , of a polymeric catalyst
  • moiety e.g. , of a solid-supported catalyst
  • the phosphorous-containing side chain e.g. , of a polymeric catalyst
  • moiety e.g. , of a solid-supported catalyst
  • the ionic monomers e.g. , of a polymeric catalyst
  • the ionic monomers can have a side chain with a cationic group that is directly connected to the polymeric backbone.
  • the ionic moieties e.g. , of a solid-supported catalyst
  • Side chains e.g. , of a polymeric catalyst directly connect to the polymeric backbone or ionic moieties (e.g. , of a solid-supported catalyst) directly attached to the solid support may can include, for example,
  • the ionic monomers (e.g. , of a polymeric catalyst) or ionic moieties (e.g. , of a solid-supported catalyst) can either all have the same cationic group, or can have different cationic groups.
  • each cationic group in the polymeric catalyst or solid-supported catalyst is a nitrogen-containing cationic group.
  • each cationic group in the polymeric catalyst or solid-supported catalyst is a phosphorous-containing cationic group.
  • the cationic group in some monomers or moieties of the polymeric catalyst or solid-supported catalyst, respectively is a nitrogen-containing cationic group, whereas the cationic group in other monomers or moieties of the polymeric catalyst or solid-supported catalyst, respectively, is a phosphorous-containing cationic group.
  • each cationic group in the polymeric catalyst or solid-supported catalyst is imidazolium.
  • the cationic group in some monomers or moieties of the polymeric catalyst or solid-supported catalyst is imidazolium, while the cationic group in other monomers or moieties of the polymeric catalyst or solid-supported catalyst is pyridinium.
  • each cationic group in the polymeric catalyst or solid-supported catalyst is a substituted phosphonium.
  • the cationic group in some monomers or moieties of the polymeric catalyst or solid-supported catalyst is triphenyl phosphonium, while the cationic group in other monomers or moieties of the polymeric catalyst or solid-supported catalyst is imidazolium.
  • the monomers in the polymeric catalyst contain both the Bronsted-Lowry acid and the cationic group in the same monomer. Such monomers are referred to as "acidic- ionic monomers”.
  • some of the moieties in the solid-supported catalyst contain both the Bronsted-Lowry acid and the cationic group in the same moieties. Such moieties are referred to as "acidic-ionic moieties”.
  • the acidic-ionic monomer e.g. , of a polymeric catalyst
  • an acidic-ionic moiety e.g. , of a solid- supported catalyst
  • the monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid-supported catalyst) include both Bronsted-Lowry acid(s) and cationic group(s), where either the Bronsted-Lowry acid is connected to the polymeric backbone (e.g. , of a polymeric catalyst) or solid support (e.g. , of a solid-supported catalyst) by a linker, and/or the cationic group is connected to the polymeric backbone (e.g. , of a polymeric catalyst) or is attached to the solid support (e.g. , of a solid-supported catalyst) by a linker.
  • the polymeric backbone e.g. , of a polymeric catalyst
  • solid support e.g. , of a solid-supported catalyst
  • any of the Bronsted-Lowry acids, cationic groups and linkers (if present) suitable for the acidic monomers/moieties and/or ionic monomers/moieties may be used in the acidic-ionic monomers/moieties.
  • the Bronsted-Lowry acid at each occurrence in the acidic- ionic monomer (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid-supported catalyst) is independently selected from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, and boronic acid.
  • the Bronsted-Lowry acid at each occurrence in the acidic-ionic monomer (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid-supported catalyst) is independently sulfonic acid or phosphonic acid.
  • the Bronsted-Lowry acid at each occurrence in the acidic-ionic monomer (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid-supported catalyst) is sulfonic acid.
  • the nitrogen-containing cationic group at each occurrence in the acidic-ionic monomer (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid-supported catalyst) is independently selected from pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyradizimium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.
  • the nitrogen- containing cationic group is imidazolium.
  • the phosphorous-containing cationic group at each occurrence in the acidic-ionic monomer (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid-supported catalyst) is independently selected from triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.
  • the phosphorous-containing cationic group is triphenyl phosphonium.
  • the polymeric catalyst or solid-supported catalyst can include at least one acidic-ionic monomer or moiety, respectively, connected to the polymeric backbone or solid support, wherein at least one acidic-ionic monomer or moiety includes at least one Bronsted-Lowry acid and at least one cationic group, and wherein at least one of the acidic-ionic monomers or moieties includes a linker connecting the acidic-ionic monomer to the polymeric backbone or solid support.
  • the cationic group can be a nitrogen-containing cationic group or a phosphorous-containing cationic group as described herein.
  • the linker can also be as described herein for either the acidic or ionic moieties.
  • the linker can be selected from unsubstituted or substituted alkyl linker, unsubstituted or substituted cycloalkyl linker, unsubstituted or substituted alkenyl linker, unsubstituted or substituted aryl linker, and unsubstituted or substituted heteroaryl linker.
  • the monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a 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 connected to the polymeric backbone or solid support, the cationic group is directly connected to the polymeric backbone or solid support, or both the Bronsted-Lowry acid and the cationic group are directly connected to the polymeric backbone or solid support.
  • the linker is unsubstituted or substituted aryl linker, or unsubstituted or substituted heteroaryl linker.
  • the linker is 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.
  • Monomers of a polymeric catalyst that have side chains containing both a Bronsted- Lowry acid and a cationic group can also be called "acidic ionomers”.
  • Acidic-ionic side chains (e.g. , of a polymeric catalyst) or acidic-ionic moieties (e.g. , of a solid-supported catalyst) that are connected by a linker can include, for example,
  • each X is independently selected from F, CI “ , Br “ , I “ , N0 2 ,N0 3 , S0 4 2” , R 7 S0 4 " , R 7 C0 2 " ,
  • S0 4 and P0 4 are each independently associated with at least two Bronsted-Lowry acids at any X position on any side chain, and each R is independently selected from hydrogen, C 1-4 alkyl, and Ci ⁇ heteroalkyl.
  • R 1 can 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 can be selected from CI “ , N0 3 " , S0 4 2- " , R 7'S0 4 - “ , and R 7'C0 2 - “ , where R 7' can be selected from hydrogen and C 1-4 alkyl. In another embodiment, each X can be selected from CI " , Br “ , ⁇ , HS0 4 " , HC0 2 " , CH 3 C0 2 " , and N0 3 “ . In other embodiments, X is acetate.
  • X is bisulfate. In other embodiments, X is chloride. In other embodiments, X is nitrate. [0158] In some embodiments, the acidic-ionic side chain (e.g. , of a polymeric catalyst) or the acidic-ionic moiety (e.g. , of a solid-supported catalyst) is independently:
  • the acidic-ionic side chain e.g. , of a polymeric catalyst
  • the acidic-ionic moiety e.g. , of a solid-supported catalyst
  • the monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid-supported catalyst) can have both a Bronsted-Lowry acid and a cationic group, where the Bronsted-Lowry acid is directly connected to the polymeric backbone or solid support, the cationic group is directly connected to the polymeric backbone or solid support, or both the Bronsted-Lowry acid and the cationic group are directly connected to the polymeric backbone or solid support.
  • Such side chains in acidic-ionic monomers (e.g. , of a polymeric catalyst) or moieties (e.g. , of a solid- supported catalyst) can include, for example,
  • the polymeric catalyst further includes hydrophobic monomers connected to form the polymeric backbone.
  • the solid-supported catalyst further includes hydrophobic moieties attached to the solid support.
  • each hydrophobic monomer or moiety has at least one hydrophobic group.
  • each hydrophobic monomer or moiety, respectively has one hydrophobic group.
  • each hydrophobic monomer or moiety has two hydrophobic groups.
  • some of the hydrophobic monomers or moieties have one hydrophobic group, while others have two hydrophobic groups.
  • each hydrophobic group is independently selected from an unsubstituted or substituted alkyl, an unsubstituted or substituted cycloalkyl, an unsubstituted or substituted aryl, and an unsubstituted or substituted heteroaryl.
  • each hydrophobic group is an unsubstituted or substituted aryl, or an unsubstituted or substituted heteroaryl.
  • each hydrophobic group is phenyl. Further, it should be understood that the hydrophobic monomers may either all have the same hydrophobic group, or may have different hydrophobic groups.
  • the hydrophobic group is directly connected to form the polymeric backbone. In some embodiments of the solid-supported catalyst, the hydrophobic group is directly attached to the solid support.
  • the acidic and ionic monomers make up a substantial portion of the polymeric catalyst. In some embodiments, the acidic and ionic moieties make up a substantial portion solid-supported catalyst. In certain embodiments, the acidic and ionic monomers or moieties make up 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 moieties of the catalyst, based on the ratio of the number of acidic and ionic monomers/moieties to the total number of monomers/moieties present in the catalyst.
  • the polymeric catalyst or solid-supported catalyst has a total amount of Bronsted-Lowry acid of between about 0.1 and about 20 mmol, between about 0.1 and about 15 mmol, between about 0.01 and about 12 mmol, between about 0.05 and about 10 mmol, between about 1 and about 8 mmol, between about 2 and about 7 mmol, between about 3 and about 6 mmol, between about 1 and about 5, or between about 3 and about 5 mmol per gram of the polymeric catalyst or solid-supported catalyst.
  • the polymeric catalyst or solid-supported catalyst at least a portion of the acidic monomers have sulfonic acid.
  • the total amount of sulfonic acid in the polymeric catalyst or solid-supported catalyst is between about 0.05 and about 10 mmol, between about 1 and about 8 mmol, or between about 2 and about 6 mmol per gram of the polymeric catalyst or solid-supported catalyst.
  • the polymeric catalyst or solid-supported catalyst at least a portion of the acidic monomers or moieties have phosphonic acid.
  • the total amount of phosphonic acid in the polymeric catalyst or solid-supported catalyst is between about 0.01 and about 12 mmol, between about 0.05 and about 10 mmol, between about 1 and about 8 mmol, or between about 2 and about 6 mmol per gram of the polymeric catalyst or solid-supported catalyst.
  • the polymeric catalyst or solid-supported catalyst at least a portion of the acidic monomers or moieties have acetic acid.
  • the total amount of acetic acid in the polymeric catalyst or solid-supported catalyst is between about 0.01 and about 12 mmol, between about 0.05 and about 10 mmol, between about 1 and about 8 mmol, or between about 2 and about 6 mmol per gram of the polymeric catalyst or solid-supported catalyst.
  • the polymeric catalyst or solid-supported catalyst at least a portion of the acidic monomers or moieties have isophthalic acid.
  • the total amount of isophthalic acid in the polymeric catalyst or solid-supported catalyst is between about 0.01 and about 5 mmol, between about 0.05 and about 5 mmol, between about 1 and about 4 mmol, or between about 2 and about 3 mmol per gram of the polymeric catalyst or solid-supported catalyst.
  • the polymeric catalyst or solid-supported catalyst at least a portion of the acidic monomers or moieties have boronic acid.
  • the total amount of boronic acid in the polymeric catalyst or solid-supported catalyst is between about 0.01 and about 20 mmol, between about 0.05 and about 10 mmol, between about 1 and about 8 mmol, or between about 2 and about 6 mmol per gram of the polymeric catalyst or solid-supported catalyst.
  • each ionic monomer further includes a counterion for each nitrogen-containing cationic group or phosphorous-containing cationic group.
  • each counterion is independently selected from halide, nitrate, sulfate, formate, acetate, or organosulfonate.
  • the counterion is fluoride, chloride, bromide, or iodide.
  • the counterion is chloride.
  • the counterion is sulfate.
  • the counterion is acetate.
  • the polymeric catalyst or solid-supported catalyst has a total amount of nitrogen-containing cationic groups and counterions or a total amount of
  • phosphorous-containing cationic groups and counterions of between about 0.01 and about 10 mmol, between about 0.05 and about 10 mmol, between about 1 and about 8 mmol, between about 2 and about 6 mmol, or between about 3 and about 5 mmol per gram of the polymeric catalyst or solid-supported catalyst.
  • the polymeric catalyst or solid-supported catalyst has at least a portion of the ionic monomers have imidazolium.
  • the total amount of imidazolium and counterions in the polymeric catalyst or solid-supported catalyst is between about 0.01 and about 8 mmol, between about 0.05 and about 8 mmol, between about 1 and about 6 mmol, or between about 2 and about 5 mmol per gram of the polymeric catalyst.
  • the polymeric catalyst or solid-supported catalyst at least a portion of the ionic monomers have pyridinium.
  • the total amount of pyridinium and counterions in the polymeric catalyst or solid-supported catalyst is between about 0.01 and about 8 mmol, between about 0.05 and about 8 mmol, between about 1 and about 6 mmol, or between about 2 and about 5 mmol per gram of the polymeric catalyst or solid- supported catalyst.
  • the polymeric catalyst or solid-supported catalyst at least a portion of the ionic monomers or moieties have triphenyl phosphonium.
  • the total amount of triphenyl phosphonium and counterions in the polymeric catalyst or solid-supported catalyst is between about 0.01 and about 5 mmol, between about 0.05 and about 5 mmol, between about 1 and about 4 mmol, or between about 2 and about 3 mmol per gram of the polymeric catalyst or solid-supported catalyst.
  • the acidic and ionic monomers make up a substantial portion of the polymeric catalyst or solid-supported catalyst. In certain embodiments, the acidic and ionic monomers or moieties make up 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
  • the ratio of the total number of acidic monomers or moieties to the total number of ionic monomers or moieties can be varied to tune the strength of the catalyst.
  • the total number of acidic monomers or moieties exceeds the total number of ionic monomers or moieties in the polymer or solid support.
  • the total number of acidic monomers or moieties is 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 or at least about 10 times the total number of ionic monomers or moieties in the polymeric catalyst or solid-supported catalyst.
  • the ratio of the total number of acidic monomers or moieties to the total number of ionic monomers or moieties 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.
  • the total number of ionic monomers or moieties exceeds the total number of acidic monomers or moieties in the catalyst. In other embodiments, the total number of ionic monomers or moieties is 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 or at least about 10 times the total number of acidic monomers or moieties in the polymeric catalyst or solid-supported catalyst.
  • the ratio of the total number of ionic monomers or moieties to the total number of acidic monomers or moieties 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.
  • the acidic monomers, the ionic monomers, the acidic-ionic monomers and the hydrophobic monomers, where present can be arranged in alternating sequence or in a random order as blocks of monomers. In some embodiments, each block has not more than twenty, fifteen, ten, six, or three monomers.
  • the monomers of the polymeric catalyst are randomly arranged in an alternating sequence.
  • the monomers are randomly arranged in an alternating sequence.
  • the monomers of the polymeric catalyst are randomly arranged as blocks of monomers.
  • the monomers are arranged in blocks of monomers.
  • each block has no more than 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, or 3 monomers.
  • the polymeric catalysts described herein can also be cross-linked.
  • Such cross-linked polymeric catalysts can be prepared by introducing cross-linking groups.
  • cross-linking can occur within a given polymeric chain, with reference to the portion of the exemplary polymeric catalysts depicted in FIGS. 4A and 4B.
  • cross- linking can occur between two or more polymeric chains, with reference to the portion of the exemplary polymeric catalysts in FIGS. 5A, 5B, 5C and 5D.
  • R 1 , R 2 and R 3 are exemplary cross linking groups.
  • Suitable cross-linking groups that can be used to form a cross-linked polymeric catalyst with the polymers described herein include, for example, substituted or unsubstituted divinyl alkanes, substituted or unsubstituted divinyl cycloalkanes, substituted or unsubstituted divinyl aryls, substituted or unsubstituted heteroaryls, dihaloalkanes, dihaloalkenes, and dihaloalkynes, where the substituents are those as defined herein.
  • cross-linking groups can include divinylbenzene, diallylbenzene, dichlorobenzene, divinylmethane, dichloromethane, divinylethane, dichloroethane,
  • the crosslinking group is divinyl benzene.
  • the polymer is cross-linked. 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 cross-linked.
  • the polymers described herein are not substantially cross-linked, such as less than about 0.9% cross-linked, less than about 0.5% cross-linked, less than about 0.1% cross-linked, less than about 0.01% cross-linked, or less than
  • the polymeric backbone is formed from one or more substituted or unsubstituted monomers.
  • Polymerization processes using a wide variety of monomers are well known in the art ⁇ see, e.g., International Union of Pure and Applied
  • the polymeric backbone is formed from one or more substituted or unsubstituted monomers selected from ethylene, propylene, hydroxyethylene, acetaldehyde, styrene, divinyl benzene, isocyanates, vinyl chloride, vinyl phenols,
  • tetrafluoroethylene butylene, terephthalic acid, caprolactam, acrylonitrile, butadiene, ammonias, diammonias, pyrrole, imidazole, pyrazole, oxazole, thiazole, pyridine, pyrimidine, pyrazine, pyradizimine, thiazine, morpholine, piperidine, piperizines, pyrollizine, triphenylphosphonate, trimethylphosphonate, triethylphosphonate, tripropylphosphonate, tributylphosphonate, trichlorophosphonate, trifluorophosphonate, and diazole.
  • the polymeric backbone of the polymeric catalysts described herein can include, for example, polyalkylenes, polyalkenyl alcohols, polycarbonates, polyarylenes,
  • the polymeric backbone can be selected from polyethylene, polypropylene, polyvinyl alcohol, polystyrene, polyurethane, polyvinyl chloride, polyphenol-aldehyde, polytetrafluoroethylene, polybutylene terephthalate, polycaprolactam, and poly(acrylonitrile butadiene styrene).
  • the polymeric backbone is polyethyelene or polypropylene.
  • the polymeric backbone is polyethylene.
  • the polymeric backbone is polyvinyl alcohol.
  • the polymeric backbone is polystyrene.
  • the polymeric backbone is polyethylene.
  • the polymeric backbone is polyvinyl alcohol.
  • polymeric backbone described herein can also include an ionic group integrated as part of the polymeric backbone.
  • Such polymeric backbones can also be called "ionomeric backbones".
  • the polymeric backbone can be selected from:
  • polyalkyleneammonium polyalkylenediammonium, polyalkylenepyrrolium,
  • polyalkyleneimidazolium polyalkylenepyrazolium, polyalkyleneoxazolium,
  • polyalkylenethiazolium polyalkylenepyridinium, polyalkylenepyrimidinium
  • polyalkylenepyrazinium polyalkylenepyradizimium, polyalkylenethiazinium,
  • polyalkylenemorpholinium polyalkylenepiperidinium, polyalkylenepiperizinium,
  • polyalkylenepyrollizinium polyalkylenetriphenylphosphonium
  • polyalkylenetrimethylphosphonium polyalkylenetriethylphosphonium
  • polyalkylenetripropylphosphonium polyalkylenetributylphosphonium
  • polyalkylenetrichlorophosphonium polyalkylenetrifluorophosphonium
  • polyalkylenediazolium polyarylalkyleneammonium, polyarylalkylenediammonium,
  • polyarylalkylenepyrrolium polyarylalkyleneimidazolium, polyarylalkylenepyrazolium, polyarylalkyleneoxazolium, polyarylalkylenethiazolium, polyarylalkylenepyridinium, polyarylalkylenepyrimidinium, polyarylalkylenepyrazinium, polyarylalkylenepyradizimium, polyarylalkylenethiazinium, polyarylalkylenemorpholinium, polyarylalkylenepiperidinium, polyarylalkylenepiperizinium, polyarylalkylenepyrollizinium,
  • polyarylalkylenetriphenylphosphonium polyarylalkylenetrimethylphosphonium
  • polyarylalkylenetriethylphosphonium polyarylalkylenetripropylphosphonium
  • polyarylalkylenetrifluorophosphonium and polyarylalkylenediazolium.
  • Cationic polymeric backbones can be associated with one or more anions, including for example F “ , CI “ , Br “ , ⁇ , N0 2 ,N0 3 , S0 4 2” , R 7 S0 4 “ , R 7 C0 2 “ , P0 4 2” , R 7 P0 3 " , and R 7 P0 2 " ' where R is selected from hydrogen, C 1-4 alkyl, and C ⁇ heteroalkyl.
  • each anion can be selected from CI “ , Br “ , ⁇ , HS0 4 " , HC0 2 " , CH C0 2 " , and N0 3 " .
  • each anion is acetate.
  • each anion is bisulfate.
  • each anion is chloride.
  • X is nitrate.
  • the polymeric backbone is alkyleneimidazolium, which refers to an alkylene moiety, in which one or more of the methylene units of the alkylene moiety has been replaced with imidazolium.
  • the polymeric backbone is selected from polyethyleneimidazolium, polyprolyeneimidazolium, and polybutyleneimidazolium.
  • monomers having heteroatoms can be combined with one or more difunctionalized compounds, such as dihaloalkanes, di(alkylsulfonyloxy)alkanes, and di(arylsulfonyloxy)alkanes to form polymers.
  • the monomers have at least two heteroatoms to link with the difunctionalized alkane to create the polymeric chain.
  • difunctionalized compounds can be further substituted as described herein.
  • the difunctionalized compound(s) can be selected from 1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, 1,2-dichlorobutane, l,3-dichlorobutane,l,4-dichlorobutane, 1,2- dichloropentane, l,3-dichloropentane,l,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-diiododo
  • the number of atoms between side chains in the polymeric backbone can vary. In some embodiments, there are between zero and twenty atoms, zero and ten atoms, zero and six atoms, or zero and three atoms between side chains attached to the polymeric backbone.
  • the polymer can be a homopolymer having at least two monomer units, and where all the units contained within the polymer are derived from the same monomer in the same manner.
  • the polymer can be a heteropolymer having at least two monomer units, and where at least one monomeric unit contained within the polymer that differs from the other monomeric units in the polymer.
  • the different monomer units in the polymer can be in a random order, in an alternating sequence of any length of a given monomer, or in blocks of monomers.
  • exemplary polymers include, for example, polyalkylene backbones that are substituted with one or more groups selected from hydroxyl, carboxylic acid, unsubstituted and substituted phenyl, halides, unsubstituted and substituted amines, unsubstituted and substituted ammonias, unsubstituted and substituted pyrroles, unsubstituted and substituted imidazoles, unsubstituted and substituted pyrazoles, unsubstituted and substituted oxazoles, unsubstituted and substituted thiazoles, unsubstituted and substituted pyridines, unsubstituted and substituted pyrimidines, unsubstituted and substituted pyrazines, unsubstituted and substituted pyradizines, unsubstituted and substituted thiazines, unsubstituted and substituted morpholines, unsubstituted and substituted and substituted
  • tributylphosphonates unsubstituted and substituted trichlorophosphonates, unsubstituted and substituted trifluorophosphonates, and unsubstituted and substituted diazoles.
  • phenyl group (-CH 2 -CH(phenyl)-CH 2 -CH(phenyl)-) is also known as polystyrene.
  • the polymer can be named a polydivinylbenzene (-CH 2 -CH(4-vinylphenyl)-CH 2 -CH(4-vinylphenyl)-).
  • heteropolymers may include those that are functionalized after polymerization.
  • One suitable example would be polystyrene-co-divinylbenzene: (-CH 2 -CH(phenyl)-
  • the polymeric backbone is a polyalkyleneimidazolium.
  • the number of atoms between side chains in the polymeric backbone can vary. In some embodiments, there are between zero and twenty atoms, zero and ten atoms, or zero and six atoms, or zero and three atoms between side chains attached to the polymeric backbone. With reference to FIG. 7A, in one exemplary embodiment, there are three carbon atoms between the side chain with the Bronsted-Lowry acid and the side chain with the cationic group. In another example, with reference to FIG. 7B, there are zero atoms between the side chain with the acidic moiety and the side chain with the ionic moiety.
  • the polymeric catalysts described herein can form solid particles.
  • a solid particle can be formed through the procedures of emulsion or dispersion polymerization, which are known to one of skill in the art.
  • the solid particles can be formed by grinding or breaking the polymer into particles, which are also techniques and methods that are known to one of skill in the art.
  • Solid particles include coating the polymers described herein on the surface of a solid core.
  • Suitable materials for the solid core can include an inert material (e.g., aluminum oxide, corn cob, crushed glass, chipped plastic, pumice, silicon carbide, or walnut shell) or a magnetic material.
  • Polymeric coated core particles can be made by dispersion polymerization to grow a cross-linked polymer shell around the core material, or by spray coating or melting.
  • solid particles include coating the polymers described herein on the surface of a solid core.
  • the solid core can be a non-catalytic support. Suitable materials for the solid core can include an inert material (e.g., aluminum oxide, corn cob, crushed glass, chipped plastic, pumice, silicon carbide, or walnut shell) or a magnetic material.
  • the solid core is made up of iron.
  • Polymeric coated core particles can be made by techniques and methods that are known to one of skill in the art, for example, by dispersion polymerization to grow a cross-linked polymer shell around the core material, or by spray coating or melting.
  • the solid supported polymer catalyst particle can have a solid core where the polymer is 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 particle can be present on or near the exterior surface of the solid particle.
  • the solid core can have an inert material or a magnetic material. In one embodiment, the solid core is made up of iron.
  • the solid particles coated with the polymer 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 particle is present on or near the exterior surface of the solid particle.
  • the solid particle is substantially free of pores, for example, having no more than about 50%, no more than about 40%, no more than about 30%, no more than about 20%, no more than about 15%, no more than about 10%, no more than about 5%, or no more than about 1% of pores.
  • Porosity can be measured by methods well known in the art, such as determining the Brunauer-Emmett-Teller (BET) surface area using the absorption of nitrogen gas on the internal and external surfaces of a material (Brunauer, S. et al., J. Am.
  • Other methods include measuring solvent retention by exposing the material to a suitable solvent (such as water), then removing it thermally to measure the volume of interior pores.
  • suitable solvent such as water
  • Other solvents suitable for porosity measurement of the polymeric catalysts include, for example, polar solvents such as DMF, DMSO, acetone, and alcohols.
  • the solid particles include a microporous gel resin. In yet other embodiments, the solid particles include a macroporous gel resin.
  • the solid particle having the polymer coating has at least one catalytic property selected from: a) disruption of at least one hydrogen bond in cellulosic materials; b) intercalation of the polymer into crystalline domains of cellulosic materials; and c) cleavage of at least one glycosidic bond in cellulosic materials.
  • the support may be selected from biochar, carbon, amorphous carbon, activated carbon, silica, silica gel, alumina, magnesia, titania, zirconia, clays (e.g., kaolinite), magnesium silicate, silicon carbide, zeolites (e.g., mordenite), ceramics, and any combinations thereof.
  • the support is carbon.
  • the support for carbon support can be biochar, amorphous carbon, or activated carbon.
  • the support is activated carbon.
  • the carbon support can have a surface area from 0.01 to 50 m 2 /g of dry material.
  • the carbon support can have a density from 0.5 to 2.5 kg/L.
  • the support can be characterized using any suitable instrumental analysis methods or techniques known in the art, including for example scanning electron microscopy (SEM), powder X-ray diffraction (XRD), Raman spectroscopy, and Fourier Transform infrared spectroscopy (FTIR).
  • SEM scanning electron microscopy
  • XRD powder X-ray diffraction
  • Raman spectroscopy Raman spectroscopy
  • FTIR Fourier Transform infrared spectroscopy
  • the carbon support can be prepared from carbonaceous materials, including for example, shrimp shell, chitin, coconut shell, wood pulp, paper pulp, cotton, cellulose, hard wood, soft wood, wheat straw, sugarcane bagasse, cassava stem, corn stover, oil palm residue, bitumen, asphaltum, tar, coal, pitch, and any combinations thereof.
  • carbonaceous materials including for example, shrimp shell, chitin, coconut shell, wood pulp, paper pulp, cotton, cellulose, hard wood, soft wood, wheat straw, sugarcane bagasse, cassava stem, corn stover, oil palm residue, bitumen, asphaltum, tar, coal, pitch, and any combinations thereof.
  • suitable methods to prepare the carbon supports used herein See e.g., 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.
  • the support is silica, silica gel, alumina, or silica-alumina.
  • silica- or alumina-based solid supports used herein. See e.g., Catalyst supports and supported catalysts, by A.B. Stiles, Butterworth Publishers, Stoneham MA, 1987.
  • the support is a combination of a carbon support, with one or more other supports selected from silica, silica gel, alumina, magnesia, titania, zirconia, clays (e.g., kaolinite), magnesium silicate, silicon carbide, zeolites (e.g., mordenite), and ceramics.
  • the polymeric catalysts and the solid-supported catalysts can include any of the Bronsted-Lowry acids, cationic groups, counterions, linkers, hydrophobic groups, cross-linking groups, and polymeric backbones or solid supports (as the case may be) described herein, as if each and every combination were listed separately.
  • the catalyst can include benzenesulfonic acid (i.e. , a sulfonic acid with a phenyl linker) connected to a polystyrene backbone or attached to the solid support, and an imidazolium chloride connected directly to the polystyrene backbone or attached directly to the solid support.
  • the polymeric catalyst can include boronyl-benzyl-pyridinium chloride (i.e. , a boronic acid and pyridinium chloride in the same monomer unit with a phenyl linker) connected to a polystyrene backbone or attached to the solid support.
  • boronyl-benzyl-pyridinium chloride i.e. , a boronic acid and pyridinium chloride in the same monomer unit with a phenyl linker
  • the catalyst can include benzenesulfonic acid and imidazolium sulfate each individually connected to a polyvinyl alcohol backbone or individually attached to the solid support.
  • the polymeric catalyst is selected from: poly [styrene-co-4-vinylbenzenesulfonic acid- co 3 -methyl- 1 -(4-vinylbenzyl)-3H- imidazol- 1 -ium chloride- codivinylbenzene] ;
  • exemplary polymers can include poly [styrene-co-4-vinylbenzene sulfonic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1 -ium nitrate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzene sulfonic acid-co-l-(4-vinylbenzyl)-3H-imidazol-l-ium iodide-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzene sulfonic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- benzoimidazol- 1-ium chloride-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzene sulfonic acid-co-3-methyl-l-(4-vinylbenzene sul
  • exemplary polymers can include poly[styrene-co-4-vinylbenzene sulfonic acid-co- 1 -(4-vinylbenzyl)-pyridinium-chloride- co-3-methyl- l-(4-vinylbenzyl)-3H-imidazol- 1-ium bisulfate-co-divinylbenzene] ; poly[styrene-co-4-vinylbenzene sulfonic acid-co- vinylbenzylchloride-co- l-methyl-2- vinyl-pyridinium bisulfate-co-divinylbenzene] ; poly(styrene-co-4-vinylbenzene phosphonic acid-co-vinylbenzyltriphenylphosphonium chloride-co -divinylbenzene) ; poly [styrene-co-4-vinylbenzene sulfonic acid-co-l-
  • exemplary polymers can include poly [styrene-co-4-vinylbenzene sulfonic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- benzoimidazol- 1-ium chloride-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzene sulfonic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1 -ium bisulfate-co-divinylbenzene] ; poly [styrene-co-4-vinylbenzene sulfonic acid-co-l-(4-vinylbenzyl)-pyridinium-bisulfate- co-divinylbenzene] ; poly(styrene-co-4-vinylbenzene sulfonic acid-co-vinylbenzylmethylimidazolium chloride-
  • exemplary polymers can include poly[styrene-co-4-vinylbenzene sulfonic acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide- co-divinyl benzene] ; poly(styrene-co-4-vinylbenzene sulfonic acid-co-vinylbenzyltriphenylphosphonium chloride-co -divinylbenzene) ; poly [styrene-co-4-vinylbenzene sulfonic acid-l-(4-vinylbenzyl)-3H-imidazol-l-ium iodide-co-divinylbenzene] ; poly[styrene-co-4-vinylbenzene sulfonic acid-co-triphenyl-(4-vinylbenzyl)-phosphonium bisulfate-co-divinylbenzene]
  • the solid-supported catalyst is selected from: amorphous carbon-supported pyrrolium chloride sulfonic acid;
  • amorphous carbon-supported triphenyl phosphonium chloride sulfonic acid amorphous carbon-supported trimethyl phosphonium chloride sulfonic acid; amorphous carbon-supported triethyl phosphonium chloride sulfonic acid; amorphous carbon-supported tripropyl phosphonium chloride sulfonic acid; amorphous carbon-supported tributyl phosphonium chloride sulfonic acid; amorphous carbon-supported trifluoro phosphonium chloride sulfonic acid; amorphous carbon-supported pyrrolium bromide sulfonic acid;
  • amorphous carbon-supported triphenyl phosphonium bromide sulfonic acid amorphous carbon-supported trimethyl phosphonium bromide sulfonic acid; amorphous carbon-supported triethyl phosphonium bromide sulfonic acid; amorphous carbon-supported tripropyl phosphonium bromide sulfonic acid; amorphous carbon-supported tributyl phosphonium bromide sulfonic acid; amorphous carbon-supported trifluoro phosphonium bromide sulfonic acid; amorphous carbon-supported pyrrolium bisulfate sulfonic acid;
  • amorphous carbon-supported pyrazolium bisulfate sulfonic acid amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon-
  • amorphous carbon-supported triphenyl phosphonium formate sulfonic acid amorphous carbon-supported trimethyl phosphonium formate sulfonic acid; amorphous carbon-supported triethyl phosphonium formate sulfonic acid; amorphous carbon-supported tripropyl phosphonium formate sulfonic acid; amorphous carbon-supported tributyl phosphonium formate sulfonic acid; amorphous carbon-supported trifluoro phosphonium formate sulfonic acid; amorphous carbon-supported pyrrolium acetate sulfonic acid;
  • amorphous carbon-supported triphenyl phosphonium acetate sulfonic acid amorphous carbon-supported trimethyl phosphonium acetate sulfonic acid; amorphous carbon-supported triethyl phosphonium acetate sulfonic acid; amorphous carbon-supported tripropyl phosphonium acetate sulfonic acid; amorphous carbon-supported tributyl phosphonium acetate sulfonic acid; amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous carbon- ⁇ supported amorphous
  • amorphous carbon-supported triphenyl phosphonium formate phosphonic acid amorphous carbon-supported trimethyl phosphonium formate phosphonic acid; amorphous carbon-supported triethyl phosphonium formate phosphonic acid; amorphous carbon-supported tripropyl phosphonium formate phosphonic acid; amorphous carbon-supported tributyl phosphonium formate phosphonic acid; amorphous carbon-supported trifluoro phosphonium formate phosphonic acid; amorphous carbon-supported pyrrolium acetate phosphonic acid;
  • amorphous carbon-supported triphenyl phosphonium acetate phosphonic acid amorphous carbon-supported trimethyl phosphonium acetate phosphonic acid; amorphous carbon-supported triethyl phosphonium acetate phosphonic acid; amorphous carbon-supported tripropyl phosphonium acetate phosphonic acid; amorphous carbon-supported tributyl phosphonium acetate phosphonic acid; amorphous carbon-supported trifluoro phosphonium acetate phosphonic acid; amorphous carbon-supported ethanoyl-triphosphonium sulfonic acid;
  • the solid-supported catalyst is selected from: activated carbon-supported pyrrolium chloride sulfonic acid;
  • activated carbon-supported pyridinium chloride sulfonic acid activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon-
  • activated carbon-supported triphenyl phosphonium bisulfate sulfonic acid activated carbon-supported trimethyl phosphonium bisulfate sulfonic acid; activated carbon-supported triethyl phosphonium bisulfate sulfonic acid; activated carbon-supported tripropyl phosphonium bisulfate sulfonic acid; activated carbon-supported tributyl phosphonium bisulfate sulfonic acid; activated carbon-supported trifluoro phosphonium bisulfate sulfonic acid; activated carbon-supported pyrrolium formate sulfonic acid;
  • activated carbon-supported imidazolium formate sulfonic acid activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activated carbon- ⁇ supported activate
  • activated carbon-supported triphenyl phosphonium acetate phosphonic acid activated carbon-supported trimethyl phosphonium acetate phosphonic acid; activated carbon-supported triethyl phosphonium acetate phosphonic acid; activated carbon-supported tripropyl phosphonium acetate phosphonic acid; activated carbon-supported tributyl phosphonium acetate phosphonic acid; activated carbon-supported trifluoro phosphonium acetate phosphonic acid; activated carbon-supported ethanoyl-triphosphonium sulfonic acid;
  • the catalysts described herein have one or more catalytic properties.
  • a "catalytic property" of a material is a physical and/or chemical property that increases the rate and/or extent of a reaction involving the material.
  • the catalytic properties can include at least one of the following properties: a) disruption of a hydrogen bond in cellulosic materials; b) intercalation of the catalyst into crystalline domains of cellulosic materials; and c) cleavage of a glycosidic bond in cellulosic materials.
  • the catalysts that have two or more of the catalytic properties described above, or all three of the catalytic properties described above.
  • the catalysts described herein have the ability to catalyze a chemical reaction by donation of a proton, and can be regenerated during the reaction process. In other embodiments, the catalysts described herein have a greater specificity for cleavage of a glycosidic bond than dehydration of a monosaccharide.
  • compositions involving the catalysts that can be used in a variety of methods described herein, including the break-down of cellulosic material.
  • compositions that include feedstock and the catalysts described herein.
  • the composition can include feedstock and an effective amount of a catalyst as described herein.
  • the composition further includes a solvent.
  • the solvent is an aqueous solvent.
  • the feedstock includes cellulose, hemicellulose, or a combination thereof.
  • compositions that include the catalysts described herein, one or more sugars, and residual feedstock.
  • the one or more sugars are one or more monosaccharides, one or more oligosaccharides, or a mixture thereof.
  • the one or more sugars are two or more sugars including at least one C4- C6 monosaccharide and at least one oligosaccharide.
  • the one or more sugars are selected from glucose, galactose, fructose, xylose, and arabinose.
  • composition that includes feedstock (e.g., softwood, hardwood, cassava, bagasse, sugarbeet pulp, straw, paper sludge, oil palm, corn stover, food waste, enzymatic digestion residuals, beer bottoms, and any combination thereof) and any of the catalysts described herein.
  • feedstock e.g., softwood, hardwood, cassava, bagasse, sugarbeet pulp, straw, paper sludge, oil palm, corn stover, food waste, enzymatic digestion residuals, beer bottoms, and any combination thereof
  • the composition further includes a solvent.
  • the composition further includes water.
  • the feedstock has cellulose, hemicellulose, or a combination thereof.
  • the feedstock also has lignin.
  • feedstock composition that includes any of the catalysts described herein, one or more sugars, and residual feedstock.
  • the one or more sugars are one or more monosaccharides, one or more
  • the one or more sugars are two or more sugars that include at least one C4-C6 monosaccharide and at least one oligosaccharide.
  • the one or more sugars are selected from glucose, galactose, fructose, xylose, and arabinose.
  • a saccharification intermediate that includes any of the catalysts described herein hydrogen-bonded to the feedstock (e.g. , softwood, hardwood, cassava, bagasse, sugarbeet pulp, straw, paper sludge, oil palm, corn stover, food waste, enzymatic digestion residuals, beer bottoms, and any combination thereof).
  • the ionic monomer or moiety of the catalyst is hydrogen-bonded to the carbohydrate alcohol groups present in cellulose, hemicellulose, and other oxygen-containing components of feedstock.
  • the acidic monomer or moiety of the catalyst is hydrogen-bonded to the carbohydrate alcohol groups present in cellulose, hemicellulose, and other oxygen-containing components of lignocellulose present in the feedstock, including the glycosidic linkages between sugar monomers.
  • the feedstock has cellulose, hemicellulose or a combination thereof.
  • sugar compositions produced from saccharification of biomass using the polymeric catalysts and solid-supported catalyst described herein.
  • Such compositions include one or more sugars.
  • the one or more sugars are one or more monosaccharides, one or more oligosaccharides, or a mixture thereof.
  • the one or more sugars are two or more sugars that include at least one C4-C6 monosaccharide and at least one oligosaccharide.
  • the one or more sugars are selected from glucose, galactose, fructose, xylose, and arabinose [0229]
  • the sugar composition may be used as a food agent.
  • the methods described herein producce a food agent from saccharification of biomass using the polymeric catalysts and solid-supported catalyst described herein.
  • the food agent may be a sweetening agent, a flavoring agent, or any combination thereof.
  • the food agent may have different aromas or flavors based on the particular mixture of sugars and organic acids in the food agent.
  • the aromas and flavors of the food agent may also vary depending on the biomass used in the methods described herein.
  • the biomass may naturally contain mineral nutrients, including for example calcium, magnesium and potassium, which also become incorporated into the food agent from hydrolysis of the biomass using the catalysts described herein.
  • the food agent may be added to a beverage, food product or a healthcare composition.
  • the food agent may be used for human consumption.
  • the food agent may be used for non-human consumption, including for example pet consumption.
  • the food agent may be used as part of agricultural feed.
  • the food agent may be mixed with grains and other inert materials, such as straw, to form animal feed.
  • Saccharification refers to the hydrolysis of cellulosic materials (e.g., biomass) into one or more sugars, by breaking down the complex carbohydrates of cellulose (and hemicellulose, where present) in the biomass.
  • the one or more sugars can be monosaccharides and/or oligosaccharides.
  • oligosaccharide refers to a compound containing two or more monosaccharide units linked by glycosidic bonds.
  • the one or more sugars are selected from glucose, cellobiose, xylose, xylulose, arabinose, mannose and galactose.
  • the cellulosic material can be subjected to a one-step or a multi-step hydrolysis process.
  • the cellulosic material is first contacted with the catalyst, and then the resulting product is contacted with one or more catalysts in a second hydrolysis reaction (e.g., using enzymes).
  • the one or more sugars obtained from hydrolysis of cellulosic material can be used in a subsequent fermentation process to produce biofuels (e.g., ethanol) and other bio-based chemicals.
  • biofuels e.g., ethanol
  • the one or more sugars obtained by the methods described herein can undergo subsequent bacterial or yeast fermentation to produce biofuels and other bio-based chemicals.
  • any method known in the art that includes pretreatment, enzymatic hydrolysis (saccharification), fermentation, or a combination thereof, can be used with the catalysts in the methods described herein.
  • the catalysts can be used before or after pretreatment methods to make the cellulose (and hemicellulose, where present) in the biomass more accessible to hydrolysis.
  • feedstocks provided for the methods described herein may be obtained from any source (including any commercially available sources), and are described in further detail below.
  • the feedstock used in the methods described herein can be selected from softwood, hardwood, cassava, bagasse, sugarbeet pulp, straw, paper sludge, oil palm, corn stover, food waste, enzymatic digestion residuals, and beer bottoms.
  • a combination of feedstocks can also be used in the methods described herein.
  • the methods can use a combination of one or more softwoods and one or more hardwoods.
  • Softwoods can include, for example, Araucaria (e.g. , Hoop Pine, Parana Pine, Chile Pine), Cedar (e.g. , red cedar, white cedar, yellow cedar), Celery Top Pine, Cypress (e.g. , Arizona Cypress, Bald Cypress, Hinoki Cypress, Lawson' s Cypress, Mediterranean Cypress), Rocky Mountain Douglas-Fir, European Yew, Fir (e.g. , Balsam Fir, Silver Fir, Noble Fir), Hemlock (e.g. , Eastern Hemlock, Mountain Hemlock, Western Hemlock), Huan Pine, Kauri, Kaya, Larch (e.g.
  • the softwood is pine.
  • Pine e.g. , Corsican Pine, Jack Pine, Lodgepole Pine, Monterey Pine, Ponderosa Pine, Red Pine, Scots Pine, White Pine (e.g. , Eastern White Pine, Western White Pine, Sugar Pine), Southern Yellow Pine (e.g. , Loblolly Pine, Longleaf Pine, Pitch Pine, Shortleaf Pine), Redcedar (e.g. , Eastern Redcedar, Western Redcedar), Redwood, Rimu, Spruce (e.g. , Norway Spruce, Black Spruce, Red Spruce, Sitka Spruce, White Spruce), Sugi, Whitecedar (e.g. , Northern Whitecedar, Southern Whitecedar), and Yellowcedar.
  • the softwood is pine.
  • Hardwoods also known as angiosperms
  • Hardwoods can include, for example, African
  • Alder e.g. , Black Alder, Red Alder
  • Applewood e.g. , Black Ash, Blue Ash, Common Ash, Green Ash, Oregon Ash, Pumpkin Ash, White Ash
  • Ash e.g. , Black Ash, Blue Ash, Common Ash, Green Ash, Oregon Ash, Pumpkin Ash, White Ash
  • Aspen e.g. , Bigtooth Aspen, European Aspen, Quaking Aspen
  • Australian Red Cedar Ayan, Balsa
  • Basswood e.g. , American Basswoord, White Basswood
  • Beech e.g. , European Beech
  • Birch e.g. , Gray Birch, River Birch, Paper Birch, Sweet Birch, Yellow Birch, Silver Birch, White Birch
  • Blackbean Blackgum, Blackwood (e.g. , Australian Blackwood, African Blackwood), Bloodwood, Bocote, Boxelder, Brazilwood, Bubinga, Buckeye (e.g. , Common Horse-Chestnut, Ohio Buckeye, Yellow Buckeye), Butternut, Camphor Laurel, Carapa, Catalpa, Cherry (e.g. , Black Cherry, Red Cherry, Whild Cherry), Chestnut (e.g. , Cape Chestnut), Coachwood, Cocobolo, Corkwood, Cottonwood (e.g.
  • Hickory e.g. , Mockernut Hickory, Pecan, Pignut Hickory, Shagbark Hickory, Shellbark Hickory), Hornbeam, Hophornbeam, Ipe, Iroko, Brazilian rosewood, Jatoba,
  • Locust e.g. , Black Locust, Yellow Locust, Honey Locust
  • Maple e.g. , Sugar Maple, Black Maple, Manitoba Maple, Red Maple, Silver Maple, Sycamore Maple
  • Oak e.g.
  • the hardwood is selected from birch, eucalyptus, aspen, maple, and any combination thereof.
  • the softwood or hardwood used in the methods described herein can be in any suitable form including, for example, chips, sawdust, bark, and any combination thereof.
  • Cassava Manihot esculenta is a woody shrub of the Euphorbiaceae (spurge family). Cassava stems can be used in the methods described herein.
  • Bagasse is the fibrous material (stalks and stems) that remains after sugarcane or sorghum stalks are crushed from juice extraction. Bagasse straw refers to the leaves of the sugarcane plant. Sugarbeet pulp is the byproduct that remains after processing the sugarbeets to extract sugar-containing juices.
  • Oil palm can include, for example, African Oil Palm, American Oil Palm, and Malaysian Oil Palm.
  • the oil palm used in the methods described heirein can be a palm oil waste material selected from empty fruit bunches, mesocarp fibre, palm kernel shell, and nut. In one embodiment, the oil palm is empty fruit bunch or mesocarp fibre.
  • Corn stover includes the leaves and stalks of maize (Zea mays).
  • Kenaf fibers include those found in the bark and core of the kenaf plant. Other fibers include wheat straw, rice straw, switch grass and miscanthus.
  • Food waste can include any food substance, in solid and/or liquid form, that is raw or cooked that is discarded or intends to be discarded.
  • Food waste includes organic residues generated by the handling, storage, sale, preparation, cooking and serving of foods.
  • Enzymatic digestion residuals can include any residual biomass materials, in solid and/or liquid form, that results from the enzymatic hydrolysis of biomass. Enzymatic digestion residuals can include residual amounts of cellulose, hemicellulose, and/or lignin.
  • Beer bottoms can include any residual materials that results from the fermentation in a beer brewing process.
  • Paper sludge includes solid residue recovered from the wastewater stream from paper and pulp mills.
  • the feedstocks used in the methods described herein include cellulosic materials, which can include any material containing cellulose and/or hemicellulose.
  • cellulosic materials which can include any material containing cellulose and/or hemicellulose.
  • cellulosic materials can be lignocellulosic materials that contain lignin in addition to cellulose and/or hemicellulose.
  • Cellulose is a polysaccharide that includes a linear chain of beta-(l-4)-D-glucose units.
  • Hemicellulose is also a polysaccharide; however, unlike cellulose, hemicellulose is a branched polymer that typically includes shorter chains of sugar units.
  • Hemicellulose can include a diverse number of sugar monomers including, for example, xylans, xyloglucans, arabinoxylans, and mannans.
  • Cellulosic materials can typically be found in biomass.
  • the methods described herein use a feedstock containing a substantial proportion of cellulosic material, such as about 5%, about 10%, about 15%, about 20%, about 25%, about 50%, about
  • cellulosic materials can include herbaceous materials, agricultural residues, forestry residues, municipal solid waste, waste paper, and pulp and paper mill residues.
  • the cellulosic material is corn stover, corn fiber, or corn cob.
  • the cellulosic material is bagasse, rice straw, wheat straw, switch grass or miscanthus.
  • cellulosic material can also include chemical cellulose (e.g., Avicel®), industrial cellulose (e.g., paper or paper pulp), bacterial cellulose, or algal cellulose.
  • chemical cellulose e.g., Avicel®
  • industrial cellulose e.g., paper or paper pulp
  • bacterial cellulose e.g., or algal cellulose.
  • the cellulosic materials can be used as obtained from the source, or can be subjected to one or pretreatments.
  • pretreated corn stover is a cellulosic material derived from corn stover by treatment with heat and/or dilute sulfuric acid, and is suitable for use with the catalysts described herein.
  • crystalline cellulose are forms of cellulose where the linear beta-(l-4)-glucan chains can be packed into a three-dimensional superstructure.
  • the aggregated beta-(l-4)-glucan chains are typically held together via inter- and intra- molecular hydrogen bonds.
  • Steric hindrance resulting from the structure of crystalline cellulose can impede access of the reactive species, such as enzymes or chemical catalysts, to the beta-glycosidic bonds in the glucan chains.
  • non-crystalline cellulose and amorphous cellulose are forms of cellulose in which individual beta-(l-4)-glucan chains are not appreciably packed into a hydrogen-bonded super- structure, where access of reactive species to the beta-glycosidic bonds in the cellulose is hindered.
  • beta-(l-4)-glucan chains present in natural cellulose exhibit a number average degree of polymerization between about 1,000 and about 4,000 anhydroglucose (“AHG") units (i.e., about 1,000-4,000 glucose molecules linked via beta- glycosidic bonds), while the number average degree of polymerization for the crystalline domains is typically between about 200 and about 300 AHG units. See e.g., R. Rinaldi, R.
  • cellulose has multiple crystalline domains that are connected by noncrystalline linkers that can include a small number of anhydroglucose units.
  • noncrystalline linkers that can include a small number of anhydroglucose units.
  • Dilute acid treatment does not appreciably disrupt the packing of individual beta-(l-4)-glucan chains into a hydrogen-bonded super- structure, nor does it hydrolyze an appreciable number of glycosidic bonds in the packed beta-(l-4)-glucan chains.
  • treatment of natural cellulosic materials with dilute acid reduces the number average degree of polymerization of the input cellulose to approximately 200-300 anhydroglucose units, but does not further reduce the degree of polymerization of the cellulose to below about 150-200 anhydroglucose units (which is the typical size of the crystalline domains).
  • the catalysts described herein can be used to digest natural cellulosic materials.
  • the catalysts can be used to digest crystalline cellulose by a chemical transformation in which the average degree of polymerization of cellulose is reduced to a value less than the average degree of polymerization of the crystalline domains. Digestion of crystalline cellulose can be detected by observing reduction of the average degree of
  • the catalysts can reduce the average degree of polymerization of cellulose from at least about 300 AGH units to less than about 200 AHG units.
  • the catalysts described herein can be used to digest crystalline cellulose, as well as microcrystalline cellulose.
  • crystalline cellulose typically has a mixture of crystalline and amorphous or noncrystalline domains
  • microcrystalline cellulose typically refers to a form of cellulose where the amorphous or non-crystalline domains have been removed by chemical processing such that the residual cellulose substantially has only crystalline domains.
  • the catalysts described herein can be used with feedstock that has been pretreated. In other embodiments, the catalysts described herein can be used with feedstock before pretreatment.
  • any pretreatment process known in the art can be used to disrupt plant cell wall components of cellulosic material, including, for example, chemical or physical pretreatment processes. See, e.g., Chandra et al., Substrate pretreatment: The key to effective enzymatic hydrolysis of lignocellulosics?, Adv. Biochem. Engin./Biotechnol. , 108: 67-93 (2007); Galbe and Zacchi, Pretreatment of lignocellulosic materials for efficient bioethanol production, Adv.
  • Suitable pretreatments can include, for example, washing, solvent-extraction, solvent- swelling, comminution, milling, steam pretreatment, explosive steam pretreatment, dilute acid pretreatment, hot water pretreatment, alkaline pretreatment, lime pretreatment, wet oxidation, wet explosion, ammonia fiber explosion, organosolvent pretreatment, biological pretreatment, ammonia percolation, ultrasound, electroporation, microwave, supercritical C02, supercritical H20, ozone, and gamma irradiation, or a combination thereof.
  • One of skill in the art would recognize the conditions suitable to pretreat biomass. See e.g., U.S. Patent Application No. 2002/0164730; Schell et al., Appl. Biochem.
  • the catalysts described herein can be used with feedstock that has not been pretreated. Further, the feedstock can also be subjected to other processes instead of or in addition to pretreatment including, for example, particle size reduction, pre-soaking, wetting, washing, or conditioning.
  • pretreatment does not imply or require any specific timing of the steps of the methods described herein.
  • the feedstock can be pretreated before hydrolysis.
  • the pretreatment can be carried out simultaneously with hydrolysis.
  • the pretreatment step itself results in some conversion of biomass to sugars (for example, even in the absence of the catalysts described herein).
  • a method for pretreating feedstock before hydrolysis of the biomass to produce one or more sugars by: a) providing feedstock; b) combining the feedstock with a disclosed catalyst for a period of time sufficient to partially degrade the feedstock; and c) pretreating the partially degraded feedstock before hydrolysis to produce one or more sugars.
  • Step b) can further include combining the feedstock and the catalyst with a solvent, such as water.
  • the feedstock of step a) can include cellulose, hemicellulose, or a combination thereof.
  • pretreating the partially degraded feedstock can include washing, solvent-extraction, solvent-swelling, comminution, milling, steam pretreatment, explosive steam pretreatment, dilute acid pretreatment, hot water pretreatment, alkaline pretreatment, lime pretreatment, wet oxidation, wet explosion, ammonia fiber explosion, organosolvent
  • pretreatment biological pretreatment, ammonia percolation, ultrasound, electroporation, microwave, supercritical C0 2 , supercritical H 2 0, ozone, and gamma irradiation, or a
  • the pretreated partially degraded biomass can be hydrolyzed to produce one or more sugars. Either chemical or enzymatic hydrolysis methods can be used.
  • the one or more sugars can include glucose, galactose, fructose, xylose, and arabinose.
  • the pretreated feedstock can be hydrolyzed using catalysts as described herein, or other methods such as chemical and enzymatic hydrolysis.
  • the sugars obtained are selected from glucose, galactose, fructose, xylose, and arabinose.
  • Feedstock containing cellulosic materials is heated to disrupt the plant cell wall components ⁇ e.g., lignin, hemicellulose, cellulose) to make the cellulose and/or hemicellulose more accessible to enzymes.
  • the feedstock is typically passed to or through a reaction vessel, where steam is injected to increase the temperature to the required temperature and pressure is retained therein for the desired reaction time.
  • the pretreatment can be performed at a temperature between about 140°C and about 230°C, between about 160°C and about 200°C, or between about 170°C and about 190°C. It should be understood, however, that the optimal temperature range for steam pretreatment can vary depending on the polymeric catalyst used.
  • the residence time for the steam pretreatment is about 1 to about 15 minutes, about 3 to about 12 minutes, or about 4 to about 10 minutes. It should be understood, however, that the optimal residence time for steam pretreatment can vary depending on the temperature range and the polymeric catalyst used.
  • steam pretreatment can be combined with an explosive discharge of the material after the pretreatment, which is known as steam explosion—a rapid flashing to atmospheric pressure and turbulent flow of the material to increase the accessible surface area by fragmentation.
  • steam explosion a rapid flashing to atmospheric pressure and turbulent flow of the material to increase the accessible surface area by fragmentation.
  • acetyl groups in hemicellulose can be cleaved, and the resulting acid can autocatalyze the partial hydrolysis of the hemicellulose to monosaccharides and/or oligosaccharides.
  • a catalyst such as sulfuric acid (typically 0.3% to 3% w/w) can be added prior to steam
  • Chemical pretreatment of feedstock can promote the separation and/or release of cellulose, hemicellulose, and/or lignin by chemical processes.
  • suitable chemical pretreatment processes include, for example, dilute acid pretreatment, lime pretreatment, wet oxidation, ammonia fiber/freeze explosion (AFEX), ammonia percolation (APR), and organosolvent pretreatments.
  • dilute or mild acid pretreatment can be employed.
  • Cellulosic material can be mixed with a dilute acid and water to form a slurry, heated by steam to a certain temperature, and after a residence time flashed to atmospheric pressure.
  • Suitable acids for this pretreatment method can include, for example, sulfuric acid, acetic acid, citric acid, nitric acid, phosphoric acid, tartaric acid, succinic acid, hydrogen chloride, or mixtures thereof.
  • sulfuric acid is used.
  • the dilute acid treatment can be conducted in a pH range of about 1-5, a pH range of about 1-4, or a pH range of about 1-3.
  • the acid concentration can be in the range from about 0.01 to about 20 wt % acid, about 0.05 to about 10 wt % acid, about 0.1 to about 5 wt % acid, or about 0.2 to about 2.0 wt % acid.
  • the acid is contacted with cellulosic material, and can be held at a temperature in the range of about 160-220°C, or about 165-195°C, for a period of time ranging from seconds to minutes (e.g., about 1 second to about 60 minutes).
  • the dilute acid pretreatment can be performed with a number of reactor designs, including for example plug-flow reactors, counter-current reactors, and continuous counter-current shrinking bed reactors.
  • an alkaline pretreatment can be employed.
  • suitable alkaline pretreatments include, for example, lime pretreatment, wet oxidation, ammonia percolation (APR), and ammonia fiber/freeze explosion (AFEX).
  • Lime pretreatment can be performed with calcium carbonate, sodium hydroxide, or ammonia at temperatures of about 85°C to about 150°C, and at residence times from about 1 hour to several days. See Wyman et al, Bioresource Technol , 96: 1959-1966 (2005); Mosier et al, Bioresource Technol, 96: 673- 686 (2005).
  • wet oxidation can be employed.
  • Wet oxidation is a thermal pretreatment that can be performed, for example, at 180°C to 200°C for 5-15 minutes with addition of an oxidative agent such as hydrogen peroxide or over-pressure of oxygen. See Schmidt and Thomsen, Bioresource Technol, 64: 139-151 (1998); Palonen et ⁇ ., ⁇ .
  • wet oxidation can be performed, for example, at about 1-40% dry matter, about 2-30% dry matter, or about 5-20% dry matter, and the initial pH can also be increased by the addition of alkali (e.g., sodium carbonate).
  • alkali e.g., sodium carbonate
  • wet explosion a combination of wet oxidation and steam explosion, can handle dry matter up to about 30%.
  • the oxidizing agent can be introduced during pretreatment after a certain residence time, and the pretreatment can end by flashing to atmospheric pressure. See WO 2006/032282.
  • pretreatment methods using ammonia can be employed.
  • ammonia fiber explosion involves treating the feedstock with liquid or gaseous ammonia at moderate temperatures (e.g., about 90-100°C) and at high pressure (e.g., about 17-20 bar) for a given duration (e.g., about 5-10 minutes), where the dry matter content can be in some instances as high as about 60%.
  • moderate temperatures e.g., about 90-100°C
  • high pressure e.g., about 17-20 bar
  • a given duration e.g., about 5-10 minutes
  • AFEX pretreatment can depolymerize cellulose, partial hydrolyze hemicellulose, and, in some instances, cleave some lignin-carbohydrate complexes.
  • an organosolvent solution can be used to delignify cellulosic material.
  • an organosolvent pretreatment involves extraction using aqueous ethanol (e.g., about 40-60% ethanol) at an elevated temperature (e.g., about 160-200°C) for a period of time (e.g., about 30-60 minutes). See Pan et al., Biotechnol. Bioeng., 90: 473-481 (2005); Pan et al., Biotechnol. Bioeng., 94: 851-861 (2006); Kurabi et al., Appl. Biochem. Biotechnol., 121: 219- 230 (2005).
  • sulfuric acid is added to the organosolvent solution as a catalyst to delignify the cellulosic material.
  • an organosolvent pretreatment can typically breakdown the majority of hemicellulose.
  • Physical pretreatment of feedstock can promote the separation and/or release of cellulose, hemicellulose, and/or lignin by physical processes.
  • suitable physical pretreatment processes can involve irradiation (e.g., microwave irradiation), steaming/steam explosion, hydrothermolysis, and combinations thereof.
  • Physical pretreatment can involve high pressure and/or high temperature.
  • the physical pretreatment is steam explosion.
  • high pressure refers to a pressure in the range of about 300-600 psi, about 350-550 psi, or about 400-500 psi, or about 450 psi.
  • high temperature refers to temperatures in the range of about 100-300°C, or about 140- 235°C.
  • the physical pretreatment is a mechanical pretreatment.
  • mechanical pretreatment can include various types of grinding or milling (e.g., dry milling, wet milling, or vibratory ball milling).
  • mechanical pretreatment is performed in a batch-process, such as in a steam gun hydrolyzer system that uses high pressure and high temperature (e.g., a Sunds Hydrolyzer available from Sunds Defibrator AB, Sweden).
  • the feedstock can be pretreated both physically and chemically.
  • the pretreatment step can involve dilute or mild acid treatment and high temperature and/or pressure treatment. It should be understood that the physical and chemical pretreatments can be carried out sequentially or simultaneously.
  • the pretreatment can also include a mechanical pretreatment, in addition to chemical pretreatment.
  • Bio pretreatment techniques can involve applying lignin-solubilizing microorganisms. See, e.g., Hsu, T.-A., Pretreatment of Biomass, in Handbook on Bioethanol: Production and Utilization, Wyman, C. E., ed., Taylor & Francis, Washington, D.C., 179-212 (1996); Ghosh and Singh, Physicochemical and biological treatments for enzymatic/microbial conversion of cellulosic biomass, Adv. Appl. Microbiol., 39: 295-333 (1993); McMillan, J. D., Pretreating lignocellulosic biomass: a review, in Enzymatic Conversion of Biomass for Fuels Production, Himmel, M.
  • pretreatment can be performed in an aqueous slurry.
  • the feedstock is present during pretreatment in amounts between about 10-80 wt , between about 20-70 wt , or between about 30-60 wt , or about 50 wt %.
  • the pretreated feedstock can be unwashed or washed using any method known in the art ⁇ e.g., washed with water) before hydrolysis to produce one or more sugars or use with the catalyst.
  • the catalyst is capable of degrading the feedstock (e.g. , softwood, hardwood, cassava, bagasse, sugarbeet pulp, straw, paper sludge, oil palm, corn stover, food waste, enzymatic digestion residuals, beer bottoms, and any combination thereof) into one or more sugars at a first-order rate constant of at least about 0.001 per hour.
  • the catalyst is capable of degrading the feedstock (e.g.
  • the catalyst is capable of converting the feedstock (e.g. , softwood, hardwood, cassava, bagasse, sugarbeet pulp, straw, paper sludge, oil palm, corn stover, food waste, enzymatic digestion residuals, beer bottoms, and any combination thereof) into one or more sugars and residual biomass, wherein the residual feedstock has a degree of polymerization of less than about 300.
  • the catalyst is capable of converting the feedstock (e.g.
  • the residual feedstock has a degree of polymerization of less than about 100, less than about 90, less than about 80, less than about 70, less than about 60, or less than about 50.
  • Saccharification is typically performed in stirred-tank reactors or vessels under controlled pH, temperature, and mixing conditions.
  • suitable processing time, temperature and pH conditions can vary depending on the type of feedstock (including the type and amount of cellulosic material in the feedstock), catalyst, and solvent used. These factors are described in further detail below.
  • a method of producing one or more sugars from feedstock by: a) providing a first composition that includes feedstock selected from softwood, hardwood, cassava, bagasse, sugarbeet pulp, straw, paper sludge, oil palm, corn stover, food waste, enzymatic digestion residuals, beer bottoms, and any combination thereof; b) providing an effective amount of a catalyst to form a reaction mixture, wherein the catalyst is a polymeric catalyst or a solid- supported catalyst, wherein the polymeric catalyst includes acidic monomers and ionic monomers connected to form a polymeric backbone, wherein a plurality of acidic monomers independently includes at least one Bronsted-Lowry acid, and wherein a plurality of ionic monomers independently includes at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or a combination thereof, wherein the solid- supported catalyst includes a solid support, acidic moieties attached to the solid support, and ionic moi
  • Also disclosed herein is a method of producing one or more sugars from feedstock, by: a) providing a first composition that includes feedstock selected from softwood, hardwood, cassava, bagasse, sugarbeet pulp, straw, paper sludge, oil palm, corn stover, food waste, enzymatic digestion residuals, beer bottoms, and any combination thereof; and b) providing an effective amount of a catalyst to form a reaction mixture, wherein the catalyst is a polymeric catalyst or a solid- supported catalyst, wherein the polymeric catalyst includes acidic monomers and ionic monomers connected to form a polymeric backbone, wherein a plurality of acidic monomers independently includes at least one Bronsted-Lowry acid, and wherein a plurality of ionic monomers independently includes at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or a combination thereof, wherein the solid- supported catalyst includes a solid support, acidic moieties attached to the solid support, and ionic moi
  • the method can further include c) degrading the feedstock in the reaction mixture to produce a liquid phase and a solid phase, wherein the liquid phase includes one or more sugars, and the solid phase includes residual feedstock.
  • the method can further include d) isolating at least a portion of the liquid phase from the solid phase; and e) recovering the one or more sugars from the isolated liquid phase.
  • the residual feedstock has at least a portion of the catalyst.
  • the catalyst can be isolated from the solid phase, either before or after isolation step d).
  • isolating a portion of the composition from the solid phase occurs substantially contemporaneously with step d).
  • substantially contemporaneously refers to two or more steps occurring during time periods that overlap 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 time.
  • the first composition can be contacted with a solvent, such as water.
  • the isolating the at least a portion of the liquid phase from the solid phase in step (d) produces a residual feedstock mixture
  • the method further includes: i) providing additional feedstock (e.g. , softwood, hardwood, cassava, bagasse, sugarbeet pulp, straw, paper sludge, sugarbeet pulp, straw, paper sludge, oil palm, corn stover, food waste, enzymatic digestion residuals, beer bottoms, and any combination thereof); ii) contacting the additional feedstock with the residual feedstock mixture; iii) degrading the additional feedstock and the residual feedstock mixture to produce a second liquid phase and a second solid phase, wherein the second liquid phase includes one or more additional sugars, and wherein the second solid phase includes additional residual feedstock; iv) isolating at least a portion of the second liquid phase from the second solid phase; and v) recovering the one or more additional sugars from the isolated second liquid phase.
  • additional feedstock e.g. , softwood, hardwood
  • the additional feedstock (e.g. , softwood, hardwood, cassava, bagasse, sugarbeet pulp, straw, paper sludge, oil palm, corn stover, food waste, enzymatic digestion residuals, beer bottoms, and any combination thereof) in step (i) is the same type or a different type as the feedstock in step (a).
  • the one or more additional sugars produced in step (iii) is the same or a different type as the one or more sugars produced in step (c).
  • the method further includes contacting the additional feedstock and the residual feedstock mixture in step (iii) with additional catalyst, in which the additional catalyst can be any of the catalysts described herein (e.g. , a polymeric catalyst, a solid-supported catalyst, or a combination thereof).
  • the additional catalyst is the same or different as the catalyst in step (b).
  • the additional feedstock mixture is combined with at least a portion of the catalyst.
  • the method further includes contacting the additional feedstock and the residual feedstock mixture with additional solvent.
  • the additional solvent is the same or different as the solvent in step (b).
  • the additional solvent includes water.
  • the second feedstock includes cellulose, hemicellulose, or a combination thereof.
  • the residual feedstock mixture includes at least a portion of the composition that has an effective amount of the polymeric catalyst.
  • the method further includes recovering the catalyst after isolating at least a portion of the second liquid phase.
  • the feedstock can be selected from softwood, hardwood, cassava, bagasse, sugarbeet pulp, straw, paper sludge, oil palm, corn stover, food waste, enzymatic digestion residuals, and beer bottoms, or any combination thereof.
  • the feedstock is softwood.
  • the feedstock is hardwood.
  • the feedstock is cassava.
  • the feedstock is bagasse.
  • the feedstock is sugarbeet pulp.
  • the feedstock is straw.
  • the feedstock is paper sludge.
  • the feedstock is oil palm.
  • the feedstock is corn stover.
  • the feedstock is food waste.
  • the feedstock is enzymatic digestion residuals.
  • the feedstock is beer bottoms.
  • the catalyst described herein has one or more catalytic properties selected from: a) disruption of a hydrogen bond in cellulosic materials;
  • the catalyst has a greater specificity for cleavage of a glycosidic bond than dehydration of a monosaccharide in cellulosic materials.
  • the feedstock includes cellulose and hemicellulose, and during the above method, the feedstock is combined with the catalyst at a temperature and at a pressure suitable to a) hydrolyze the cellulose to a greater extent than the hemicellulose, or
  • the additional feedstock and the residual feedstock mixture are combined with a second catalyst as disclosed herein.
  • the additional feedstock and the residual feedstock mixture are combined with a second solvent, such as water.
  • the second feedstock has at least a portion of the composition that has an effective amount of the catalyst. This composition, or a portion thereof, can be isolated from the additional residual feedstock. The portion can be isolated from the second solid phase, either before or after step iv). In some embodiments, isolating a portion of the composition from the second solid phase occurs substantially contemporaneously with step iv).
  • the one or more sugars produced in these methods can be selected from one or more monosaccharides, one or more oligosaccharides, or a combination thereof.
  • the one or more monosaccharides can include one or more C4-C6 monosaccharides.
  • the monosaccharides can be selected from glucose, galactose, fructose, xylose, and arabinose.
  • saccharification can last up to about 200 hours.
  • the feedstock can be in contact with the catalyst from about 1 to about 96 hours, from about 12 to about 72 hours, or from about 12 to about 48 hours.
  • the feedstock can be in contact with the polymer at temperature in the range of about 25°C to about 150°C. In other embodiments, the feedstock can be in contact with the polymer in the range of about 30°C to about 125°C, about 30°C to about 140°C, about 80°C to about 120°C, about 80°C to about 130°C, about 100°C to 110°C, or about 100°C to about 130°C.
  • the pH for saccharification is generally affected by the intrinsic properties of the catalyst used.
  • the acidic moiety of the catalyst can affect the pH of saccharification.
  • the use of sulfuric acid moiety in a catalyst results in
  • saccharification at a pH of about 3. In other embodiments, saccharification is performed at a pH between about 0 and about 6.
  • the reacted effluent typically has a pH of at least about 4, or a pH that is compatible with other processes such as enzymatic treatment. It should be understood, however, that the pH can be modified and controlled by the addition of acids, bases or buffers.
  • the pH can vary within the reactor. For example, high acidity at or near the surface of the catalyst can be observed, whereas regions distal to the catalyst surface can have a substantially neutral pH. Thus, one of skill would recognize that determination of the solution pH should account for such spatial variation.
  • the saccharification methods described herein can further include monitoring the pH of the saccharification reaction, and optionally adjusting the pH within the reactor.
  • a low pH in solution can indicate an unstable catalyst, in which the catalyst can be losing at least a portion of its acidic groups to the surrounding environment through leaching.
  • the pH near the surface of the catalyst is below about 7, below about 6, or below about 5. Amount of feedstock used
  • the amount of the feedstock used in the methods described herein relative to the amount solvent used can affect the rate of reaction and yield.
  • the amount of the cellulosic material used can be characterized by the dry solids content.
  • dry solids content refers to the total solids of a slurry as a percentage on a dry weight basis.
  • the dry solids content of the cellulosic materials is between about 5 wt % to about 95 wt %, between about 10 wt% to about 80 wt %, between about 15 wt % to about 75 wt %, or between about 15 wt % to about 50 wt %.
  • the amount of the polymeric catalysts used in the saccharification methods described herein can depend on several factors including, for example, the type of cellulosic material, the concentration of the cellulosic material, the type and number of pretreatment(s) applied to the cellulosic material, and the reaction conditions ⁇ e.g., temperature, time, and pH).
  • the weight ratio of the catalyst to the cellulose material is about O. lg/g to about 50 g/g, about O.
  • an effective amount of the polymeric catalysts disclosed herein refers to an amount sufficient to degrade biomass to, for instance, attain one or more desired factor levels listed above.
  • the effective amount is the amount of catalyst that would degrade more than about 5%, more than about 10%, more than about 20%, more than about 30%, more than about 40%, or more than about 50%.
  • the effective amount can be any of the weight ratio ranges listed above.
  • hydrolysis using the catalyst is carried out in an aqueous environment.
  • aqueous solvent is water, which can be obtained from various sources. Generally, water sources with lower concentrations of ionic species are useful, as such ionic species can reduce effectiveness of the catalyst.
  • the aqueous solvent includes water, the water has less than about 10% of ionic species ⁇ e.g., salts of sodium, phosphorous, ammonium, magnesium, or other species found naturally in lignocellulosic biomass).
  • the saccharification methods described herein can further include monitoring the amount of water present in the saccharification reaction and/or the ratio of water to biomass over a period of time.
  • the saccharification methods described herein can further include supplying water directly to the reaction, for example, in the form of steam or steam condensate.
  • the hydration conditions in the reactor are such that the water-to-cellulosic material ratio is about 5: 1, about 4: 1, about 3: 1, about 2: 1, about 1: 1, about
  • Saccharification can be performed in a batch process or a continuous process.
  • saccharification is performed in a batch process, where the contents of the reactor are continuously mixed or blended, and all or a substantial amount of the products of the reaction are removed.
  • saccharification is performed in a batch process, where the contents of the reactor are initially intermingled or mixed but no further physical mixing is performed.
  • saccharification is performed in a batch process, wherein once further mixing of the contents, or periodic mixing of the contents of the reactor, is performed (e.g., at one or more times per hour), all or a substantial amount of the products of the reaction are removed after a certain period of time.
  • saccharification is performed in a continuous process, where the contents flow through the reactor with an average continuous flow rate but with no explicit mixing. After introduction of the catalyst and the feedstock into the reactor, the contents of the reactor are continuously or periodically mixed or blended, and after a period of time, less than all of the products of the reaction are removed.
  • saccharification is performed in a continuous process, where the mixture containing the catalyst and feedstock is not actively mixed. Additionally, mixing of catalyst and feedstock can occur as a result of the redistribution of catalysts settling by gravity, or the non-active mixing that occurs as the material flows through a continuous reactor. Reactors
  • the reactors used for the saccharification methods described herein can be open or closed reactors suitable for use in containing the chemical reactions described herein.
  • Suitable reactors can include, for example, a fed-batch stirred reactor, a batch stirred reactor, a continuous flow stirred reactor with ultrafiltration, a continuous plug-flow column reactor, an attrition reactor, or a reactor with intensive stirring induced by an electromagnetic field. See e.g., 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, 25: 33-38 (2003); Gusakov, A.
  • reactor types can include, for example, fluidized bed, upflow blanket, immobilized, and extruder type reactors for hydrolysis and/or fermentation.
  • the reactor can include a continuous mixer, such as a screw mixer.
  • the reactors can be generally fabricated from materials that are capable of withstanding the physical and chemical forces exerted during the processes described herein. In some embodiments, such materials used for the reactor are capable of tolerating high concentrations of strong liquid acids; however, in other embodiments, such materials can not be resistant to strong acids.
  • the reactor can be filled with cellulosic material by a top-load feeder containing a hopper capable of holding cellulosic material.
  • the reactor typically contains an outlet means for removal of contents (e.g., a sugar-containing solution) from the reactor.
  • contents e.g., a sugar-containing solution
  • the outlet means of the reactor is linked to a continuous incubator into which the reacted contents are introduced.
  • the outlet means provides for removal of residual cellulosic material by, e.g., a screw feeder, by gravity, or a low shear screw.
  • the use of the catalysts described herein can increase the rate and/or yield of saccharification.
  • the ability of the catalyst to hydrolyze the cellulose and hemicellulose components of biomass to soluble sugars can be measured by determining the effective first- order rate constant,
  • the catalysts described herein are capable of degrading biomass into one or more sugars at a first-order rate constant of at least about 0.001 per hour, at least about 0.01 per hour, at least about 0.1 per hour, at least about 0.2 per hour, at least about 0.3 per hour, at least about 0.4 per hour, at least about 0.5 per hour, or at least about 0.6 per hour.
  • the hydrolysis yield of the cellulose and hemicellulose components of feedstock to soluble sugars by the catalyst can be measured by determining the degree of polymerization of the residual biomass. The lower the degree of polymerization of the residual biomass, the greater the hydrolysis yield.
  • the catalysts described herein are capable of converting feedstock into one or more sugars and residual biomass, wherein the residual biomass has a degree of polymerization of less than about 300, less than about 250, less than about 200, less than about 150, less than about 100, less than about 90, less than about 80, less than about 70, less than about 60, or less than about 50. d) Separation and Purification of the Sugars
  • the methods for producing one or more sugars from the feedstock using the catalysts described herein further include recovering the sugars that are produced from the hydrolysis of the feedstock.
  • the method for producing one or more sugars from the feedstock using the catalyst described herein further includes recovering the degraded or converted feedstock.
  • the sugars which are typically soluble, can be separated from the insoluble residual feedstock using technology well known in the art such as, for example, centrifugation, filtration, and gravity settling.
  • Separation of the sugars can be performed in the hydrolysis reactor or in a separator vessel.
  • the method for producing one or more sugars from the feedstock is performed in a system with a hydrolysis reactor and a separator vessel. Reactor effluent containing the monosaccharides and/or oligosaccharides is transferred into a separator vessel and is washed with a solvent (e.g. , water), by adding the solvent into the separator vessel and then separating the solvent in a continuous centrifuge.
  • a solvent e.g. , water
  • a reactor effluent containing residual solids is removed from the reactor vessel and washed, for example, by conveying the solids on a porous base (e.g. , a mesh belt) through a solvent (e.g. , water) wash stream. Following contact of the stream with the reacted solids, a liquid phase containing the monosaccharides and/or oligosaccharides is generated.
  • a cyclone Suitable types of cyclones used for the separation can include, for example, tangential cyclones, spark and rotary separators, and axial and multi-cyclone units.
  • separation of the sugars is performed by batch or continuous differential sedimentation.
  • Reactor effluent is transferred to a separation vessel, optionally combined with water and/or enzymes for further treatment of the effluent.
  • solid biomaterials e.g. , residual treated biomass
  • the catalyst, and the sugar-containing aqueous material can be separated by differential sedimentation into a plurality of phases (or layers).
  • the catalyst layer can sediment to the bottom, and depending on the density of the residual biomass, the biomass phase can be on top of, or below, the aqueous phase.
  • the phases are sequentially removed, either from the top of the vessel or an outlet at the bottom of the vessel.
  • the separation vessel When the phase separation is performed in a continuous mode, the separation vessel contains one or more than one outlet means (e.g. , two, three, four, or more than four), generally located at different vertical planes on a lateral wall of the separation vessel, such that one, two, or three phases are removed from the vessel.
  • the removed phases are transferred to subsequent vessels or other storage means.
  • the catalyst and/or biomass can be separately washed by the aqueous layer to remove adhered sugar molecules.
  • the sugars isolated from the vessel can be subjected to further processing steps (e.g., as in drying, fermentation) to produce biofuels and other bio-products.
  • the monosaccharides that are isolated can be at least about 1% pure, at least about 5% pure, at least about 10% pure, at least about 20% pure, at least about 40% pure, at least about 60% pure, at least about 80% pure, at least about 90% pure, at least about 95% pure, at least about 99% pure, or greater than about 99% pure, as determined by analytical procedures known in the art, such as determination by high performance liquid chromatography (HPLC), functionalization and analysis by gas chromatography, mass spectrometry, spectrophotometric procedures based on chromophore complexation and/or carbohydrate oxidation-reduction chemistry.
  • HPLC high performance liquid chromatography
  • mass spectrometry mass spectrometry
  • spectrophotometric procedures based on chromophore complexation and/or carbohydrate oxidation-reduction chemistry.
  • the residual biomass isolated from the vessels can be useful as a combustion fuel or as a feed source of non-human animals such as livestock. e) Recovery of the Catalysts
  • the catalysts used for saccharification of biomass can be recovered and reused.
  • Sedimentation of the catalyst is used to recover the catalyst following use.
  • the catalyst can sink, while other residuals solids can remain suspended in the saccharification reaction mixture.
  • Residual feedstock and residual feedstock mixtures can include, for example, remaining feedstock after a digestion process, unreactive material in the feedstock, catalyst (e.g. , intact catalyst that was used in the process to generate the residual feedstock and/or catalyst in which some fraction of the counter-ions have been exchanged with salts that were present in the feedstock), digestion byproducts (e.g. , lignin), one or more sugars, one or more sugar degradation products, and water or other solvents.
  • the sedimentation rate can be measured by the sedimentation coefficient
  • the sedimentation rate of the catalyst can, in some embodiments, be about 10 ⁇ 6 - 10 ⁇ 2 , about 10 ⁇ 5 -10 ⁇ 3 , or about 10 ⁇ 4 -10 ⁇ 3 .
  • the density of the catalyst can also have an impact on its ease of recovery from saccharification.
  • the gravimetric density of the catalyst is about 0.5-3.0 kg/L, about 1.0-3.0 kg/L, or about 1.1-3.0 kg/L.
  • One of skill in the art would recognize that various methods and techniques suitable for measuring the density of a catalyst as described herein.
  • the sugars obtained from hydrolysis of cellulosic material using the polymeric catalysts and solid-supported catalyst described herein can be used in downstream processes to produce biofuels and other bio-based chemicals.
  • the one or more sugars obtained from hydrolysis of cellulosic material using the catalysts described herein can be fermented to produce one or more downstream products (e.g., ethanol and other biofuels, vitamins, lipids, proteins).
  • the saccharide composition can undergo fermentation to produce one or more difunctional compounds.
  • difunctional compounds can have an n-carbon chain, with a first functional group and a second functional group.
  • the first and second functional groups can be independently selected from -OH, -NH 2 , -COH, and -COOH.
  • the difunctional compounds can include, for example, alcohols, carboxylic acids, hydroxyacids, or amines.
  • Exemplary difunctional alcohols can include ethylene glycol, 1,3- propanediol, and 1,4-butanediol.
  • Exemplary difunctional carboxylic acids can include succinic acid, adipic acid, and pimelic acid.
  • Exemplary difunctional hydroxyacids can include glycolic acid and 3-hydroxypropanoic acid.
  • Exemplary difunctional amines can include 1,4- diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane.
  • the methods described herein include contacting the saccharide composition with a fermentation host to produce a fermentation product mixture that can include ethylene glycol, succinic acid, adipic acid, or butanediol, or a combination thereof.
  • a fermentation host can include ethylene glycol, succinic acid, adipic acid, or butanediol, or a combination thereof.
  • the difunctional compounds can be isolated from the fermentation product mixture, and/or further purified. Any suitable isolation and purification techniques known in the art can be used. b) Fermentation Host
  • the fermentation host can be bacteria or yeast. In one embodiment, the fermentation host is bacteria. In some embodiments, the bacteria are classified in the family of
  • Enterobacteriaceae examples include Aranicola, Arsenophonus, Averyella, Biostraticola, Brenneria, Buchnera, Budvicia, Buttiauxella, Candidatus,
  • Curculioniphilus Cuticobacterium, Candidatus Ishikawaella, Macropleicola, Phlomobacter, Candidatus Riesia, Candidatus Stammerula, Cedecea, Citrobacter, Cronobacter, Dickeya, Edwardsiella, Enterobacter, Erwinia, Escherichia, Ewingella, Grimontella, Hafnia, Klebsiella, Kluyvera, Leclercia, Leminorella, Margalefia, Moellerella, Morganella, Obesumbacterium, Pantoea, Pectobacterium, Photorhabdus, Phytobacter, Plesiomonas, Pragia, Proteus,
  • the bacteria are Escherichia coli (E. coli).
  • the fermentation host is genetically modified.
  • the fermentation host is genetically modified E. coli.
  • the fermentation host is genetically modified E. coli.
  • fermentation host can be genetically modified to enhance the efficiency of specific pathways encoded by certain genes.
  • the fermentation host can be modified to enhance expression of endogenous genes that can positively regulate specific pathways.
  • the fermentation host can be further modified to suppress expression of certain endogenous genes.
  • saccharification can be combined with fermentation in a separate or a simultaneous process.
  • the fermentation can use the aqueous sugar phase or, if the sugars are not substantially purified from the reacted biomass, the fermentation can be performed on an impure mixture of sugars and reacted biomass.
  • Such methods include, for example, separate hydrolysis and fermentation (SHF), simultaneous saccharification and fermentation (SSF), simultaneous saccharification and cofermentation (SSCF), hybrid hydrolysis and fermentation (HHF), separate hydrolysis and co-fermentation (SHCF), hybrid hydrolysis and co- fermentation (HHCF), and direct microbial conversion (DMC).
  • SHF separate hydrolysis and fermentation
  • SSF simultaneous saccharification and fermentation
  • SSCF simultaneous saccharification and cofermentation
  • HHF hybrid hydrolysis and fermentation
  • SHCF separate hydrolysis and co-fermentation
  • HHCF hybrid hydrolysis and co- fermentation
  • DMC direct microbial conversion
  • SHF uses separate process steps to first enzymatically hydrolyze cellulosic material to fermentable sugars (e.g., glucose, cellobiose, cellotriose, and pentose sugars), and then ferment the sugars to ethanol.
  • fermentable sugars e.g., glucose, cellobiose, cellotriose, and pentose sugars
  • SSCF involves the cofermentation of multiple sugars. See Sheehan, J., and Himmel, M., Enzymes, energy and the environment: A strategic perspective on the U.S. Department of Energy's research and development activities for bioethanol, Biotechnol. Prog., 15: 817-827 (1999).
  • HHF involves a separate hydrolysis step, and in addition a simultaneous
  • saccharification and hydrolysis step which can be carried out in the same reactor.
  • the steps in an HHF process can be carried out at different temperatures; for example, high temperature enzymatic saccharification followed by SSF at a lower temperature that the fermentation strain can tolerate.
  • DMC combines all three processes (enzyme production, hydrolysis, and
  • the polymeric catalysts described herein can be made using polymerization techniques known in the art, including for example techniques to initiate polymerization of a plurality of monomer units. [0346] In some embodiments, the polymeric catalysts described herein can be formed by first forming an intermediate polymer functionalized with the ionic group, but is free or substantially free of the acidic group. The intermediate polymer can then be functionalized with the acidic group.
  • the polymeric catalysts described herein can be formed by first forming an intermediate polymer functionalized with the acidic group, but is free or substantially free of the ionic group.
  • the intermediate polymer can then be functionalized with the ionic group.
  • the polymeric catalysts described herein can be formed by polymerizing monomers with both acidic and ionic groups.
  • the starting polymer is selected from polyethylene, polypropylene, polyvinyl alcohol, polycarbonate, polystyrene, polyurethane, or a combination thereof.
  • the starting polymer is a polystyrene.
  • the starting polymer is poly(styrene-co-vinylbenzylhalide-co-divinylbenzene).
  • the starting polymer is poly(styrene-co-vinylbenzylchloride-co-divinylbenzene).
  • the nitrogen-containing compound is selected from a pyrrolium compound, an imidazolium compound, a pyrazolium compound, an oxazolium compound, a thiazolium compound, a pyridinium compound, a pyrimidinium compound, a pyrazinium compound, a pyradizimium compound, a thiazinium compound, a morpholinium compound, a piperidinium compound, a piperizinium compound, and a pyrollizinium compound.
  • the nitrogen- containing compound is an imidazolium compound.
  • the phosporus-containing compound is selected from a triphenyl phosphonium compound, a trimethyl phosphonium compound, a triethyl phosphonium compound, a tripropyl phosphonium compound, a tributyl phosphonium compound, a trichloro phosphonium compound, and a trifluoro phosphonium compound.
  • the acid is selected from sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid and boronic acid. In one embodiment, the acid is sulfuric acid.
  • the ionic salt is selected from lithium chloride, lithium bromide, lithium nitrate, lithium sulfate, lithium phosphate, sodium chloride, sodium bromide, sodium sulfate, sodium hydroxide, sodium phosphate, potassium chloride, potassium bromide, potassium nitrate, potassium sulfate, potassium phosphate, ammonium chloride, ammonium bromide, ammonium phosphate, ammonium sulfate, tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, di-methylimidazolium chloride, methylbutylimidazoliumchloride, di-methylmorpholinium chloride, zinc (II) chloride, zinc (II) bromide, magnesium (II) chloride, and calcium (II) chloride.
  • the polystyrene is poly(styrene-co-vinylbenzylhalide-co- divinylbenzene). In one embodiment, the polystyrene is poly(styrene-co-vinylbenzylchloride- co-divinylbenzene) .
  • the polymer has one or more catalytic properties selected from: a) disruption of at least one hydrogen bond in cellulosic materials; b) intercalation of the polymer into crystalline domains of cellulosic materials; and c) cleavage of at least one glycosidic bond in cellulosic materials.
  • the polymers described herein can be made, for example, on a scale of at least about 100 g, at least about 1 kg, at least about 20 kg, at least about 100 kg, at least about 500 kg, or at least about 1 ton in a batch or continuous process.
  • the solid-supported catalysts described herein with carbon supports can be prepared by subjecting a carbonaceous material to: (1) support preparation, (2) support activation, and (3) support functionalization.
  • An exemplary preparation sequence is provided in Table 1.
  • One of skill in the art would recognize that two or more of the support preparation, support activation, and catalyst functionalization steps can be combined into a single step.
  • Table 1 Exemplary steps for preparing a dual-functionalized solid carbon supported catalyst
  • Support preparation can be accomplished by any methods known in the art. For example, pyrolysis can be used to convert a carbonaceous material into a carbon support.
  • Incomplete carbonization can also be employed to obtain a carbon support.
  • a carbonaceous material can be subjected to an oxygen-deficient atmosphere at a controlled temperature to produce a carbon support.
  • commercially-available carbon supports can be used.
  • the carbonaceous material can be naturally-occurring. Suitable carbonaceous materials can include, for example, shrimp shell, chitin, coconut shell, wood pulp, paper pulp, cotton, cellulose, hard wood, soft wood, wheat straw, sugarcane bagasse, cassava stem, corn stover, oil palm residue, bitumen, asphaltum, tar, coal, pitch, or any combinations thereof.
  • the carbon content of the carbonaceous material is greater than about 20% g carbon / g dry material, greater than about 30% g carbon / g dry material, or greater than about 40% g carbon / g dry material.
  • the carbonaceous material can also contain oxygen, nitrogen, or a combination thereof.
  • carbon support 802 can have one or more functional groups, including for example hydroxyl, amino and carboxyl groups.
  • the oxygen content of the carbonaceous material is between about 10% to about 60% g oxygen / g dry material, between about 20% to about 40% g oxygen / g dry material, or between about 20% to about 30% g oxygen / g dry material.
  • the nitrogen content of the carbonaceous material is greater than about 1% g nitrogen / g dry material, greater than about 5% g nitrogen / g dry material, or greater than about 10% g nitrogen / g dry material.
  • the carbonaceous material is carbonized in an atmosphere containing less than about 20% oxygen, less than about 10% oxygen, less than about 1% oxygen, less than about 1 part per thousand of oxygen, less than about 100 parts per million of oxygen, or less than about 10 parts per million of oxygen.
  • the carbonaceous material is carbonized in an atmosphere containing nitrogen.
  • the carbonaceous material is carbonized in an atmosphere containing purified nitrogen.
  • the carbonaceous material is carbonized at a temperature between about 200°C and about 500°C, between about 250°C and about 400°C, or between about
  • the temperature can be controlled to within plus or minus about 50°C, within plus or minus about 10°C, within plus or minus about 5°C, or to within plus or minus about 2°C.
  • the carbonaceous material is carbonized within about 2 to about 10 hours, within about 2 to about 5 hours, within about 3 to about 5 hours, or within about
  • the carbonaceous material can undergo incomplete carbonization based on the carbonization conditions described above. Incomplete carbonization transforms the
  • the superstructure can include, for example, poly-condensed fused ring sub- structures that are attached to one another with random orientation to form the overall superstructure.
  • Heteroatoms such as oxygen and nitrogen present in the carbonaceous starting material, become incorporated into the superstructure.
  • Some of the heteroatoms can be incorporated into the carbon support, as saturated, unsaturated, and aromatic heterocycles, many of which can be fused rings.
  • the carbon support and hence the final solid-supported catalyst
  • Some of the heteroatoms in the solid-supported catalyst can also be from the moieties attached to the carbon support.
  • oxygen can be from alcohol moieties (e.g., phenol, alcohols) and carboxylic acid moieties (e.g. , formic, formyl, acetic, acetyl) covalently bonded to the edge of the heterocyclic sub-structures.
  • Nitrogen can be from amino moieties (e.g. , aniline, alkylamino).
  • the heteroatom content of the carbon support can affect the reactivity in
  • the heteroatoms incorporated into the superstructure can affect the electronic nature of the carbon support, and hence its reactivity with the functional moieties.
  • the carbonaceous materials that can be used to prepare the carbon support can, in some embodiments, contain: about 30% - about 70% g carbon / g starting material; about 2% - about 8% g hydrogen / g starting material; about 0% - about 60% g oxygen / g starting material; and about 0% - about 60% g oxygen / g starting material.
  • the heteroatom content of the carbon support can in some embodiments, contain: about 0-40%, about 5-30%, about 10-30%, or about 15-30% g oxygen / g backbone; and about 0-15%, about 2-
  • the overall heteroatom content of the solid-supported catalyst can vary depending in part on the functional moieties attached to the solid support.
  • haloacylation or haloalkylation can introduce the oxygen and/or halogen content.
  • Quaternization (alkylation) can introduce the phosphorous and/or nitrogen content.
  • Sulfonation can increase the sulfur and oxygen content.
  • the solid-supported catalyst can contain: about 10-50%, about 15-40%, about 10-30% g oxygen /g catalyst; about 0-15%, about 2-10%, about 5-10% g nitrogen /g catalyst; about 5-20%, about 5-15%, or about 10-15% g sulfur/g catalyst; and about 5-20%, about 5-15%, about 8-15% g phosphorous/g catalyst.
  • the carbon supports prepared according to the methods described above can be used in combination with other solid supports, including for example silica, silica gel, alumina, magnesia, titania, zirconia, clays, magnesium silicate, silicon carbide, zeolites, and ceramics.
  • solid supports including for example silica, silica gel, alumina, magnesia, titania, zirconia, clays, magnesium silicate, silicon carbide, zeolites, and ceramics.
  • Support activation step involves subjecting the carbon support to a chemical functionalization reaction to attach reactive linkers to the carbon support.
  • Suitable reactive linkers can include, for example, haloalkanes, haloacyl compounds, amines, and diazo compounds. Such reactive linkers activate the carbon support, making the support more susceptible to further functionalization to attach acidic, ionic, acidic-ionic and/or hydrophobic moieties.
  • the reactive linker can be introduced to the carbon support by a halomethylating agent.
  • the reactive linker can be introduced to the carbon support by a chloromethylating agent.
  • the chloromethylating agent is chloromethyl methyl ether.
  • the reactive linker can be introduced to the carbon support by a haloacylating agent.
  • the reactive linker can be introduced to the carbon support by a chloroacylating agent.
  • a suitable example of a chloroacylating agent is chloroacetyl chloride.
  • the Lewis acid catalyst is selected from zinc (II) chloride, aluminum (III) chloride, and iron (III) chloride.
  • the Lewis acid can be zinc chloride (ZnCl 2 ) or aluminum chloride (AICI3).
  • the reactive linker can be introduced to the carbon support via a Friedel-Crafts alkylation or a Friedel-Crafts acylation reaction.
  • An exemplary reaction to introduce such a reactive linker to the carbon support is depicted in FIG. 8A.
  • the chloromethylating or chloroacylating reaction can be performed in an inert solvent.
  • suitable inert solvents can include any solvent that is suitable for a Friedel-Crafts reaction.
  • suitable inert solvents can include, for example, dichloromethane (DCM), dichloroethane (DCE), diethyl ether, tetrahydrofuran (THF), or ionic liquids.
  • the chloromethylation or chloroacylation reaction can be performed at a temperature below about 25°C, below about 10°C, below about 5°C, or at or below about 0°C.
  • activated carbon support 804 has a chloromethane moiety as the reactive linker.
  • other halo moieties can be added as a reactive linker, and a plurality of reactive linkers can be attached to the activated carbon support.
  • the activated solid supports can undergo one or more reactions to attach acidic and/or ionic moieties to the solid support.
  • activated carbon support 804 is first quaternized to attach a nitrogen-containing cationic group to the solid support.
  • the exemplary nitrogen-containing cationic group in FIG. 8B has a formula NR X R 2 R 3 , wherein each
  • R 1 , R2 and R 3 is independently hydrogen or alkyl, or R 1 is taken together with R 2 and the nitrogen atom to which they are attached to form a heterocycloalkyl, or R 1 , R2 and R 3 are taken together with the nitrogen atom to which they are attached to form a heteroaryl.
  • Quaternized solid support 806 undergoes acid-treatment to produce dual- functionalized solid supported catalyst 808. While only one cationic group and one acidic group is depicted in catalyst 808 of FIG. 8B, it should be understood that a plurality of cationic groups and a plurality of acidic groups can be attached to the solid support using the methods described herein. [0380] In other embodiments, the activated solid support can be acidified before
  • the activated support can be functionalized with an acidic-ionic group.
  • one or more other functional groups can be attached to the solid-supported catalysts, including hydrophobic groups.
  • a catalyst comprising acidic monomers and ionic monomers connected to form a polymeric backbone, wherein each acidic monomer independently comprises at least one Bronsted-Lowry acid, and wherein each ionic monomer independently comprises at least one nitrogen-containing cationic group, at least one phosphorous-containing cationic group, or a combination thereof.
  • each linker is independently selected from the group consisting of unsubstituted or substituted alkyl linker, unsubstituted or substituted cycloalkyl linker, unsubstituted or substituted alkenyl linker, unsubstituted or substituted aryl linker, unsubstituted or substituted heteroaryl linker, unsubstituted or substituted alkyl ether linker, unsubstituted or substituted alkyl ester linker, and unsubstituted or substituted alkyl carbamate linker. 7.
  • 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.
  • L is a an unsubstituted alkyl linker, alkyl linker substituted with oxo, unsubstituted cycloalkyl linker, unsubstituted aryl linker, unsubstituted heterocycloalkyl linker, and unsubstituted heteroaryl linker; and r is 1 to 3.
  • each nitrogen-containing cationic group is independently selected from the group consisting of pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyradizimium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium; and each phosphorous-containing cationic group is independently selected from the group consisting of triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium
  • L is a an unsubstituted alkyl linker, alkyl linker substituted with oxo, unsubstituted cycloalkyl linker, unsubstituted aryl linker, unsubstituted heterocycloalkyl linker, and unsubstituted heteroaryl linker; and each R la , R lb and R lc is independently hydrogen or alkyl; or R la and R lb are taken together with the nitrogen atom to which they are attached to form an unsubstituted
  • R a and R , 1 1b D are taken together with the nitrogen atom to which they are attached to form an unsubstituted heteroaryl or substituted heteroaryl, and R c is absent; r is 1 to 3; and
  • X is F, CI “ , Br “ , ⁇ , N0 2 ,N0 3 , S0 4 2 ⁇ , R 7 S0 4 ⁇ , R 7 C0 2 , P0 4 2" , R 7 P0 3 , R 7 P0 2 " , S0 4 2" and
  • each R la , R lb and R lc is independently hydrogen or alkyl; or R la and R lb are taken together with the nitrogen atom to which they are attached to form an unsubstituted
  • R la and R lb are taken together with the nitrogen atom to which they are attached to form an unsubstituted heteroaryl or substituted heteroaryl, and R lc is absent; s is an integer; v is 0 to 10; and
  • X is F, CI “ , Br “ , ⁇ , N0 2 ,N0 3 , S0 4 2 ⁇ , R 7 S0 4 ⁇ , R 7 C0 2 , P0 4 2" , R 7 P0 3 , R 7 P0 2 " , S0 4 2" and
  • polymeric backbone 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),
  • polyalkyleneammonium polyalkylenediammonium, polyalkylenepyrrolium,
  • polyalkyleneimidazolium polyalkylenepyrazolium, polyalkyleneoxazolium,
  • polyalkylenethiazolium polyalkylenepyridinium, polyalkylenepyrimidinium
  • polyalkylenepyrazinium polyalkylenepyradizimium, polyalkylenethiazinium,
  • polyalkylenemorpholinium polyalkylenepiperidinium, polyalkylenepiperizinium,
  • polyalkylenepyrollizinium polyalkylenetriphenylphosphonium
  • polyalkylenetrimethylphosphonium polyalkylenetriethylphosphonium
  • polyalkylenetripropylphosphonium polyalkylenetributylphosphonium
  • polyalkylenetrichlorophosphonium polyalkylenetrifluorophosphonium
  • a catalyst comprising a solid support, acidic moieties attached to the solid support, and ionic moieties attached to the solid support, wherein the solid support comprises a material, wherein the material is selected from the group consisting of carbon, silica, silica gel, alumina, magnesia, titania, zirconia, clays, magnesium silicate, silicon carbide, zeolites, ceramics, and any combinations thereof,
  • each acidic moiety independently has at least one Bronsted-Lowry acid, and wherein each ionic moiety independently has at least one nitrogen-containing cationic group or at least one phosphorous-containing cationic group, or a combination thereof.
  • 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 Bronsted-Lowry acid is independently sulfonic acid or phosphonic acid.
  • each linker is independently selected from the group consisting of unsubstituted or substituted alkyl linker, unsubstituted or substituted cycloalkyl linker, unsubstituted or substituted alkenyl linker, unsubstituted or substituted aryl linker, unsubstituted or substituted heteroaryl linker, unsubstituted or substituted alkyl ether linker, unsubstituted or substituted alkyl ester linker, and unsubstituted or substituted alkyl carbamate linker.
  • L is a an unsubstituted alkyl linker, alkyl linker substituted with oxo, unsubstituted cycloalkyl linker, unsubstituted aryl linker, unsubstituted heterocycloalkyl linker, and unsubstituted heteroaryl linker; and r is 1 to 3.
  • each ionic moiety is selected from the group consisting of pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyradizimium, thiazinium, morpholinium, piperidinium, piperizinium, pyrollizinium, phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, triphenyl phosphonium and trifluoro phosphonium.
  • each nitrogen-containing cationic group is independently selected from the group consisting of pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyradizimium, thiazinium, morpholinium, piperidinium,
  • each phosphorous-containing cationic group is independently selected from the group consisting of triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.
  • each linker is independently selected from the group consisting of unsubstituted or substituted alkyl linker, unsubstituted or substituted cycloalkyl linker, unsubstituted or substituted alkenyl linker, unsubstituted or substituted aryl linker, unsubstituted or substituted heteroaryl linker, unsubstituted or substituted alkyl ether linker, unsubstituted or substituted alkyl ester linker, and unsubstituted or substituted alkyl carbamate linker.
  • each ionic moiety is independently selected from the group consisting of:
  • L is a an unsubstituted alkyl linker, alkyl linker substituted with oxo, unsubstituted cycloalkyl linker, unsubstituted aryl linker, unsubstituted heterocycloalkyl linker, and unsubstituted heteroaryl linker; and each R la , R lb and R lc is independently hydrogen or alkyl; or R la and R lb are taken together with the nitrogen atom to which they are attached to form an unsubstituted
  • R la and R lb are taken together with the nitrogen atom to which they are attached to form an unsubstituted heteroaryl or substituted heteroaryl, and R lc is absent; r is 1 to 3; and
  • X is F, CI “ , Br “ , T, N0 2 ,N0 3 , S0 4 2 ⁇ , R 7 S0 4 ⁇ , R 7 C0 2 , P0 4 2" , R 7 P0 3 , R 7 P0 2 " , S0 4 2" and
  • each hydrophobic moiety is selected from the group consisting of an unsubstituted or substituted alkyl, an unsubstituted or substituted cycloalkyl, an unsubstituted or substituted aryl, and an unsubstituted or substituted heteroaryl.
  • each acidic-ionic moiety comprises a Bronsted- Lowry acid and a cationic group.
  • each Bronsted- Lo wry acid is independently selected from the group consisting of sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, boronic acid, and perfluorinated acid.
  • each cationic group is independently a nitrogen- containing cationic group or a phosphorous-containing cationic group.
  • each nitrogen-containing cationic group is independently selected from pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyradizimium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium; and each phosphorous-containing cationic group is independently selected from triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.
  • each linker is independently selected from unsubstituted or substituted alkyl linker, unsubstituted or substituted cycloalkyl linker, unsubstituted or substituted alkenyl linker, unsubstituted or substituted aryl linker, unsubstituted or substituted heteroaryl linker, unsubstituted or substituted alkyl ether linker, unsubstituted or substituted alkyl ester linker, and unsubstituted or substituted alkyl carbamate linker.
  • 151 46 The catalyst of any one of embodiments 18 to 45, wherein the material is carbon, and wherein the carbon is selected from the group consisting of biochar, amorphous carbon, and activated carbon.

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Abstract

La présente invention concerne des catalyseurs utilisés dans le cadre de processus de saccharification non-enzymatiques. Les catalyseurs peuvent être des catalyseurs polymères ou des catalyseurs à support solide dotés de fractions acides et ioniques. L'invention concerne également des procédés d'hydrolyse de matériaux cellulosiques en monosaccharides et/ou oligosaccharides à l'aide des catalyseurs de la présente invention.
PCT/US2013/056389 2012-08-24 2013-08-23 Catalyseurs polymères et à support solide, et procédés de digestion de matériaux cellulosiques utilisant lesdits catalyseurs WO2014031956A1 (fr)

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EP13831228.5A EP2888044A4 (fr) 2012-08-24 2013-08-23 Catalyseurs polymères et à support solide, et procédés de digestion de matériaux cellulosiques utilisant lesdits catalyseurs
KR1020157007481A KR20150047583A (ko) 2012-08-24 2013-08-23 중합체 촉매와 고체-지지된 촉매, 및 이러한 촉매를 사용하여 셀룰로오스 물질을 분해하는 방법
US14/423,697 US20150202607A1 (en) 2012-08-24 2013-08-23 Polymeric and solid-supported catalysts, and methods of digesting cellulosic materials using such catalysts
CN201380055050.3A CN104736245B (zh) 2012-08-24 2013-08-23 高分子催化剂和固载化催化剂、以及使用该催化剂消化纤维素材料的方法
CA2922254A CA2922254A1 (fr) 2012-08-24 2013-08-23 Catalyseurs polymeres et a support solide, et procedes de digestion de materiaux cellulosiques utilisant lesdits catalyseurs

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US61/693,200 2012-08-24
US61/693,210 2012-08-24
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US13/831,495 US9238845B2 (en) 2012-08-24 2013-03-14 Methods of producing sugars from biomass feedstocks

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