WO2019079136A1

WO2019079136A1 - Processes for making polymer gels and porous carbonaceous materials therefrom

Info

Publication number: WO2019079136A1
Application number: PCT/US2018/055786
Authority: WO
Inventors: Shahid P. Qureshi; Cornel Hagiopol
Original assignee: Georgia-Pacific Chemicals Llc
Priority date: 2017-10-16
Filing date: 2018-10-14
Publication date: 2019-04-25

Abstract

Processes for making polymer gels and porous carbonaceous material therefrom. In some examples, a process for making a polymer gel can include reacting a first reaction mixture that can include a phenolic monomer, an aldehyde monomer, and a first catalyst to produce a prepolymer. A second catalyst can be combined with the prepolymer to produce a second reaction mixture. The second reaction mixture can include greater than 30 wt% of the second catalyst based on a weight of the phenolic monomer. The prepolymer can be polymerized to produce the polymer gel at a temperature of at least 95°C in less than 25 minutes, as measured according to ASTM D2471-99.

Description

PROCESSES FOR MAKING POLYMER GELS AND POROUS CARBONACEOUS

MATERIALS THEREFROM

BACKGROUND Field

[0001] Embodiments described generally relate to processes for making polymer gels and porous carbonaceous materials therefrom.

Description of the Related Art

[0002] Porous carbonaceous materials are used in the manufacture of a variety of products, such as supercapacitors. Such porous carbonaceous materials can be produced by converting polymer gels into the desired porous carbonaceous material. For example, aromatic alcohols and aldehydes can be used to make prepolymers, and the prepolymers can then be processed into large monolithic polymer gels or polymer particles in gel form by polymerization and these polymer gels can be converted to porous carbonaceous materials via pyrolysis.

[0003] Monolithic polymer gels and polymer particles in gel form, however, are difficult and expensive to produce. For example, a significant amount of energy, long process time, and specialized equipment is typically required to polymerize the prepolymer and produce the polymer gels. There is a need, therefore, for improved processes for making polymer gels and polymer particles in gel form and porous carbonaceous material therefrom.

SUMMARY

[0004] Processes for making polymer gels and porous carbonaceous material therefrom are provided. In some examples, a process for making a polymer gel can include reacting a first reaction mixture that can include a phenolic monomer, an aldehyde monomer, and a first catalyst to produce a prepolymer. A second catalyst can be combined with the prepolymer to produce a second reaction mixture. The second reaction mixture can include greater than 30 wt% of the second catalyst based on a weight of the phenolic monomer. The prepolymer can be polymerized to produce the polymer gel at a temperature of at least 95°C in less than 25 minutes, as measured according to ASTM D2471-99.

[0005] In other examples, a process for making a polymer gel can include reacting a first reaction mixture that can include a phenolic monomer and formaldehyde in the presence of a first catalyst to produce a prepolymer. The phenolic monomer can include phenol, a first dihydroxybenzene or a mixture thereof. A second catalyst can be combined with the prepolymer to produce a second reaction mixture. The second reaction mixture can include greater than 30 wt% of the second catalyst based on a weight of the phenolic monomer. The second catalyst can include an anhydride, a second dihydroxybenzene, or a mixture thereof. The prepolymer can be polymerized at a temperature of at least 95°C to produce the polymer gel in less than 25 minutes, as measured according to ASTM D2471-99.

[0006] In other examples, a process for making a polymer gel can include reacting a first reaction mixture that can include a phenolic monomer and aldehyde monomer in the presence of a first catalyst to produce a prepolymer. The prepolymer can be combined with a second catalyst and a carrier fluid to produce a second reaction mixture. The second reaction mixture can include greater than 30 wt% of the second catalyst based on a weight of the phenolic monomer. The prepolymer can be polymerized to produce polymer particles in gel form. The prepolymer can be polymerized to produce polymer particles in gel form at a temperature of at least 95°C, in less than 25 minutes, as measured according to ASTM D2471-99.

DETAILED DESCRIPTION

[0007] Polymer gels, e.g., monolithic polymer gels and/or polymer particles in gel form, can be produced by polymerizing one or more phenolic monomers and one or more aldehyde monomers in the presence of one or more first catalysts. For example, the phenolic monomer and the aldehyde monomer can be mixed, blended, or otherwise combined with the first catalyst to produce a first reaction mixture and the first reaction mixture can be reacted to form or otherwise produce a prepolymer. The prepolymer can be mixed, blended, or otherwise combined with a second catalyst to produce a second reaction mixture. The prepolymer in the second reaction mixture can be polymerized to produce the polymer gel. In some examples, the second reaction mixture can also include a carrier fluid. For example, if the second reaction mixture includes the carrier fluid, the prepolymer and second catalyst can be suspended or emulsified in the carrier fluid. The prepolymer can be polymerized in the suspension or emulsion to produce polymer particles in gel form.

[0008] It has been surprisingly and unexpectedly discovered that when the second reaction mixture includes greater than 30 wt% of the second catalyst, based on a weight of the phenolic monomer, the prepolymer can polymerize to produce the polymer gel or polymer particles in gel form, in significantly less time as compared to when the second catalyst is present in a reduced amount, e.g., 25 wt% or less, based on the weight of the phenolic monomer. For example, it was surprisingly and unexpectedly discovered that the polymer gel can be produced in less than 25 minutes when the second reaction mixture is heated at a temperature of 95°C or greater, as measured according to ASTM D2471-99.

[0009] In one or more examples, the polymer gel and/or polymer particles in gel form can be further processed by heating the polymer gel and/or polymer particles in gel form at a temperature of about 600°C to about 1,800°C for about 30 seconds to about 10 hours to produce a porous carbonaceous material. In one or more examples, the polymer gel and/or polymer particles in gel form can be further processed by heating the polymer gel and/or polymer particles in gel form at a temperature of about 25°C to about 150°C to produce a thermoset polymer. In one or more examples, the polymer gel and/or polymer particles in gel form can be further processed by contacting the polymer gel and/or polymer particles in gel form with a fluid including water, alcohol or a mixture thereof to produce a washed polymer gel; and drying the washed polymer gel and/or polymer particles in gel form to produce a dried polymer gel.

[0010] As used herein, the term "carrier fluid" refers to any a suspension fluid, diluent, dispersion fluid, emulsion fluid, and/or the continuous phase of a suspension, dispersion, and/or emulsion. As used herein, the terms "suspension", "slurry", and "dispersion" are used interchangeably and refer to a plurality of solids distributed within a liquid medium. In one or more examples, the polymer gel and/or polymer particles in gel form can be heated at a temperature of about 25°C to about 150°C for a time sufficient to produce the thermoset polymer. Crosslinking refers to the structural and/or morphological change that occurs in the prepolymer and/or polymer, such as by covalent chemical reaction, ionic interaction or clustering, phase transformation or inversion, and/or hydrogen bonding.

[0011] As used herein, the terms "polymer particulates in gel form" and "polymer particles in gel form" are used interchangeably and refer to a network of polymer chains that have one or more pores or voids therein, and a liquid at least partially occupies or fills the one or more pores or voids. As used herein, the term "dried polymer gel" refers to a network of polymer chains having one or more pores or voids therein and a gas at least partially occupying or filling the one or more pores or voids. In one or more examples, a dried polymer gel can be produced by further processing a polymer gel by contacting the polymer gel with a fluid comprising water, alcohol or a mixture thereof to produce a washed polymer gel; and drying the washed polymer gel.

[0012] The components of the first reaction mixture, i.e., the phenolic monomer, the aldehyde monomer, and the first catalyst can be combined with one another in any order or sequence. For example, the phenolic monomer, the aldehyde monomer, and the first catalyst can be added sequentially to a reactor vessel. . In another example, the phenolic monomer, the aldehyde monomer, and the first catalyst can be simultaneously combined with one another.

[0013] In one or more examples, the phenolic monomer, the aldehyde monomer, and the first catalyst can be in the form of a slurry, suspension, or dispersion in a liquid medium. Illustrative liquid mediums can be or include, but are not limited to, water, one or more alcohols, hydrocarbon solvents or a mixture thereof. Illustrative alcohols can be or include, but are not limited to, methanol, ethanol, propanol, isopropanol, butanol, and the like, and mixtures thereof. Illustrative hydrocarbons can be or include, but are not limited to, acetone, tetrahydrofuran, benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, or mixtures thereof. In one or more examples, the polymerization of the phenolic monomer and the aldehyde monomer can produce water as a liquid medium.

[0014] The first reaction mixture can include about 5 wt% to 95 wt%, of the liquid medium based on the combined weight of the liquid medium, the phenolic monomer, the aldehyde monomer, and the first catalyst. In one or more examples, The first reaction mixture can include about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, or about 45 wt% to about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, or about 95 wt%, of the liquid medium based on the combined weight of the liquid medium, the phenolic monomer, the aldehyde monomer, and the first catalyst.

[0015] Illustrative phenolic monomers can be or include, but are not limited to, one or more substituted phenolic monomers, one or more unsubstituted phenolic monomers, or any mixture of substituted and/or unsubstituted phenolic monomers. In some examples, suitable phenolic monomers can be represented by Formula I:

Formula I

[0016] where R¹ and are R² are independently selected from hydrogen (H), a hydroxy group, Cl-5 alkyl, or OR3, where R3 is a Cl-5 alkyl or Cl-5 aryl, and where at least one of R¹ and R² is a hydroxy group. Other suitable phenolic monomers can be represented by Formula II:

Formula II

[0017] where R_a, Rb, Rc, and Rd are independently hydrogen (H); a hydroxy; a halide, e.g., fluoride, chloride, bromide or iodide; a nitro; a benzo; a carboxy; an acyl, e.g. , formyl; an alkyl - carbonyl, e.g., acetyl, and an arylcarbonyl, e.g., benzoyl; an alkyl, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like; an alkenyl, e.g., an unsubstituted or substituted vinyl, unsubstituted or substituted methacrylate, unsubstituted or substituted acrylate; silyl ether; siloxanyl; aryl e.g., phenyl and naphthyl; aralkyl e.g., benzyl; or alkaryl e.g., alkylphenyls. In some examples, at least two of R_a, Rc, and Rd can be hydrogen.

[0018] In some examples the phenolic monomer can be or include phenol,/^'.e., mono-hydroxy benzene. In other examples, the phenolic monomer can be or include, but are not limited to, alkyl-substituted phenols e.g., cresols and xylenols; cycloalkyl-substituted phenols e.g., cyclohexyl phenol; alkenyl-substituted phenols; aryl -substituted phenols e.g., p-phenyl phenol; alkoxy-substituted phenols e.g., 3,5-dimethyoxyphenol; aryloxy phenols e.g., p-phenoxy phenol; and halogen- substituted phenols e.g., p-chlorophenol. Dihydric phenols or dihydroxybenzenes e.g., catechol, resorcinol, hydroquinone, bisphenol A, bisphenol F, or any mixture thereof can also be used. In particular, the phenol component can include phenol; alkyl-substituted phenols e.g., the cresols and xylenols; cycloalkyl-substituted phenols e.g., cyclohexyl phenol; alkenyl-substituted phenols; aryl -substituted phenols e.g., p-phenyl phenol; alkoxy-substituted phenols e.g., 3,5-dimethyoxyphenol; aryloxy phenols e.g., p-phenoxy phenol; halogen-substituted phenols e.g., p-chlorophenol; catechol, hydroquinone, bisphenol A and bisphenol F. In another example, the phenolic monomer can be or include resorcinol, phenol, catechol, hydroquinone, pyrogallol, 5-methylresorcinol, 5-ethylresorcinol, 5- propylresorcinol, 4-methylresorcinol, 4-ethylresorcinol, 4-propylresorcinol, resorcinol monobenzoate, resorcinol monosinate, resorcinol diphenyl ether, resorcinol monomethyl ether, resorcinol monoacetate, resorcinol dimethyl ether, phloroglucinol, benzoylresorcinol, resorcinol rosinate, alkyl substituted resorcinol, aralkyl substituted resorcinol, 2- methylresorcinol, phloroglucinol, 1,2,4-benzenetriol, 3,5-dihydroxybenzaldehyde, 2,4- dihydroxybenzaldehyde, 4-ethylresorcinol, 2,5-dimethylresorcinol, 5-methylbenzene-l,2,3- triol, 3,5-dihydroxybenzyl alcohol, 2,4,6-trihydroxytoluene, 4-chlororesorcinol, 2', 6'- dihydroxyacetophenone, 2',4'-dihydroxyacetophenone, 3',5'-dihydroxyacetophenone, 2,4,5- trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 3,5- dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 1,3- dihydroxynaphthalene, 2',4'-dihydroxypropiophenone, 2',4'-dihydroxy-6'- methylacetophenone, l-(2,6-dihydroxy-3-methylphenyl)ethanone, 3-methyl 3,5- dihydroxybenzoate, methyl 2,4-dihydroxybenzoate, gallacetophenone, 2,4-dihydroxy-3- methylbenzoic acid, 2,6-dihydroxy-4-methylbenzoic acid, methyl 2,6-dihydroxybenzoate, 2- methyl-4-nitroresorcinol, 2,4,5-trihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, 2,3,4- trihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, 2-nitrophloroglucinol or any mixture thereof. Another suitable phenolic monomer can be or include phloroglucinol.

[0019] In at least one example, the phenolic monomer can be or include, but is not limited to, phenol, resorcinol, i.e., 1,3-dihydroxybenzene, or a mixture thereof. In another example, the phenolic monomer can be a polyhydroxybenzene, a dihydroxybenzene, a trihydroxybenzene, or any mixture thereof. The phenolic monomer can include any combination of two or more phenolic monomers combined with one another and/or added independent of one another to the reaction mixture.

[0020] In one or more examples, the phenolic monomer can be or include resorcinol (i.e., benzene-l,3-diol). In some examples, the resorcinol can be provided as a resorcinol- formaldehyde copolymer. Liquid resorcinol-formaldehyde copolymers can have a Brookfield viscosity at 25°C that varies widely. For example, liquid resorcinol-formaldehyde copolymer scan have Brookfield viscosity at 25°C ranging from a low of about 5 centipoise (cP), about 50 cP, about 100 cP, about 200 cP, about 400 cP, or about 600 cP to a high of about 1,000 cP, about 2,500 cP, about 5,000 cP, about 10,000 cP, about 15,000 cP, or about 20,000 cP. Liquid resorcinol copolymers typically have a dark amber color.

[0021] The first reaction mixture can include about 5 wt% to about 50 wt% of the phenolic monomer, based on the combined weight of the liquid medium, the phenolic monomer, the aldehyde monomer, and the first catalyst. For example, the first reaction mixture can include about 5 wt%, about 10 wt%, about 15 wt%, or about 20 wt% to about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, or about 50 wt% of the phenolic monomer, based on the combined weight of the liquid medium, the phenolic monomer, the aldehyde monomer, and the first catalyst. In another example, the first reaction mixture can include at least 5 wt%, at least 7 wt%, at least 10 wt%, at least 13 wt%, at least 15 wt%, at least 17 wt%, at least 20 wt%, or at least 23 wt% and up to about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, or about 50 wt% of the phenolic monomer, based on the combined weight of the liquid medium, the phenolic monomer, the aldehyde monomer, and the first catalyst.

[0022] In one or more examples, the phenolic monomer can be partially or completely replaced with one or more resins. Illustrative resins can be or include, but are not limited to, a polyethylene, a polypropylene, an ethylene vinyl acetate, an ethylene ethyl acrylate, polyurethane, natural polymers, a styrene-isoprene-styrene, an acrylonitrile-butadiene-styrene, a styrene-butadiene-styrene, a polystyrene, a polyurethane, an acrylic polymer, a polyvinyl chloride, a fluoroplastic, a pine rosin (e.g., tall oil rosin, wood rosin, and gum rosin), a modified rosin (e.g., disproportionated rosins, hydrogenated rosins, polymerized or oligomerized rosins, Diels-Alder rosin adducts), a rosin ester (e.g., hydrogenated rosin esters, polymerized rosin esters, phenolic-modified rosin esters, dibasic acid-modified rosin esters; the rosin esters can be derived from tall oil rosin, wood rosin, and/or gum rosin), a polysulfide, a styrene- acrylonitrile, a nylon, a phenol-formaldehyde novolac resin, or any combination or mixture thereof. Other illustrative resins can include, but are not limited to, oligomers of C₅ hydrocarbons (e.g., oligomers of cyclopentadiene), oligomers of C hydrocarbons (e.g., oligomers of alpha-methyl styrene and vinyl toluene, often referred to as aromatic hydrocarbon tackifiers), terpene resins (e.g., oligomers of terpenes such as alpha-pinene, beta-pinene, and limonene), oligomeric reaction products of terpenes and phenolics, coumarone-indene resins, oligomeric reaction products of terpenes and styrenics, cycloaliphatic resins (e.g., dicyclopentadiene-based resins), crude tall oil, distilled tall oil, or any combination or mixture thereof. The resin, if present, can be added prior to polymerization, during polymerization, and/or after polymerization has been completed.

[0023] The one or more aldehyde monomers can be or include one or more substituted aldehyde monomers, one or more unsubstituted aldehyde monomers, or any mixture thereof. Illustrative aldehyde monomers can be represented by the formula RCHO, where R is hydrogen or a hydrocarbon moiety. Illustrative hydrocarbon radicals can include from 1 to about 8 carbon atoms. In another example, suitable aldehyde monomer can also include the so-called masked aldehydes or aldehyde equivalents, e.g., acetals or hemiacetals. Illustrative aldehyde compounds can be or include, but are not limited to, formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfuraldehyde, benzaldehyde, or any combination or mixture thereof. One or more other aldehydes, such as glyoxal can be used in place of or in combination with formaldehyde and/or other aldehydes. In at least one example, the aldehyde compound can include formaldehyde, UFC, or a mixture thereof.

[0024] The aldehyde monomer can be used as a solid, liquid, and/or gas. Considering formaldehyde in particular, the formaldehyde can be or include paraform (solid, polymerized formaldehyde), formalin solutions (aqueous solutions of formaldehyde, sometimes with methanol, in 37 percent, 44 percent, or 50 percent formaldehyde concentrations), Urea- Formaldehyde Concentrate ("UFC"), and/or formaldehyde gas in lieu of or in addition to other forms of formaldehyde can also be used. In another example, the aldehyde can be or include a pre-reacted urea-formaldehyde mixture having a urea to formaldehyde weight ratio of about 1 :2 to about 1 :3.

[0025] In some examples, the aldehyde monomer can be or include, but is not limited to, one or more multifunctional aldehyde compounds. As used herein, the terms "multifunctional aldehyde compound" and "multifunctional aldehyde" are used interchangeably and refer to compounds having at least two functional groups, with at least one of the functional groups being an aldehyde group. For example, the multifunctional aldehyde can include two or more aldehyde functional groups. In another example, the multifunctional aldehyde can include at least one aldehyde functional group and at least one functional group other than an aldehyde functional group. As used herein, the term "functional group" refers to reactive groups in the multifunctional aldehyde compound and can include, but is not limited to, aldehyde groups, carboxylic acid groups, ester groups, amide groups, imine groups, epoxide groups, aziridine groups, azetidinium groups, and hydroxyl groups. [0026] The multifunctional aldehyde compound can include two or more carbon atoms and have two or more aldehyde functional groups. For example, the multifunctional aldehyde compound can include two, three, four, five, six, or more carbon atoms and have two or more aldehyde functional groups. The multifunctional aldehyde compound can include two or more carbon atoms and have at least one aldehyde functional group and at least one functional group other than an aldehyde group such as a carboxylic acid group, an ester group, an amide group, an imine groups, an epoxide group, an aziridine group, an azetidinium group, and/or a hydroxyl group. For example, the multifunctional aldehyde compound can include two, three, four, five, six, or more carbon atoms and have at least one aldehyde functional group and at least one functional group other than an aldehyde group such as a carboxylic acid group, an ester group, an amide group, an imine groups, an epoxide group, an aziridine group, an azetidinium group, and/or a hydroxyl group.

[0027] Suitable bifunctional or difunctional aldehyde compounds that include three (3) or more carbon atoms and have two aldehyde functional groups (-CHO) can be represented by the following formula:

o o

li II

a— c—— c— H

[0028] where R is a divalent aliphatic, cycloaliphatic, aromatic, or heterocyclic group having from 1 to 12 carbon atoms. Illustrative multi-functional aldehydes can include, but are not limited to, malonaldehyde, succinaldehyde, glutaraldehyde, 2-hydroxyglutaraldehyde, β- methylglutaraldehyde, adipaldehyde, pimelaldehyde, suberaldehyde, malealdehyde, fumaraldehyde, sebacaldehyde, phthalaldehyde, isophthal aldehyde, terephthal aldehyde, ring- substituted aromatic aldehydes, or any mixture thereof. A suitable bifunctional or difunctional aldehyde that includes two carbon atoms and has two aldehyde functional groups is glyoxal.

[0029] Illustrative multifunctional aldehyde compounds that include an aldehyde group and a functional group other than an aldehyde group can be or include, but are not limited to, glyoxylic acid, glyoxylic acid esters, glyoxylic acid amides, 5-(hydroxymethyl)furfural, or any combination or mixture thereof. The aldehyde group in the multifunctional aldehyde compound can exist in other forms, e.g., as a hydrate. As such, any form or derivative of a particular multifunctional aldehyde compound can be used to prepare the binder compositions discussed and described herein. For example, in the context of glyoxylic acid, glyoxylic acid, glyoxylic acid monohydrate, and/or glyoxylate can be combined with the tannins and the Lewis acid to produce the binder composition.

[0030] The first reaction mixture can include about 3 wt% to about 70 wt% of the aldehyde monomer, based on the combined weight of the liquid medium, the phenolic monomer, the aldehyde monomer, and the first catalyst. In one or more examples, the first reaction mixture can include about 3 wt%, about 5 wt%, about 7 wt%, about 10 wt%, about 15 wt%, or about 20 wt% to about 30 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, or about 70 wt%, of the aldehyde monomer based on the total weight of the liquid medium, the phenolic monomer(s), the aldehyde monomer(s), and the first catalyst. In one or more examples, the first reaction mixture can include at least 3 wt%, at least 5 wt%, at least 7 wt%, at least 10 wt%, at least 13 wt%, at least 15 wt%, at least 17 wt%, at least 20 wt%, at least 23 wt%, or at least 25 wt% and up to about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, or about 70 wt%, of the aldehyde monomer based on the combined weight of the liquid medium, the phenolic monomer, the aldehyde monomer, and the first catalyst.

[0031] If any one or more of the components discussed and described herein include two or more different compounds, those two or more different compounds can be present in any ratio with respect to one another. For example, if the phenolic monomer includes a first phenolic monomer and a second phenolic monomer, the phenolic monomer can have a concentration of the first phenolic monomer be from about 1 wt% to about 99 wt% and conversely about 99 wt% to about 1 wt% of the second phenolic monomer, based on the total weight of the first and second phenolic monomer. In another example, the amount of the first phenolic monomer can be about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt% about 30 wt%, about 35 wt%, about 40 wt%, or about 45 wt% to about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, or about 95 wt%, based on the total weight of the first and second phenolic monomer. When the catalyst, and/or liquid medium includes two or more different compounds, those two or more different compounds can be present in similar amounts as the first and second phenolic monomer.

[0032] The first catalyst can also be referred to as an initiator, a reducer, and/or an accelerator. In some examples, the first catalyst can be unconsumed by the polymerization reaction. In some examples, the first catalyst can be partially consumed by the polymerization reaction. In other examples, the first catalyst can be consumed by the polymerization reaction. For example, consumption or at least partial consumption of the first catalyst can include the first catalyst reacting with the phenolic monomer, the aldehyde monomer, the second catalyst (upon the addition thereof), the prepolymer, itself, or any combination thereof. The first catalyst can be or include one or more amines and/or one or more metal catalysts. Illustrative first catalysts can be or include, but are not limited to ammonia, dimethylethanolamine (DMEA), ethylenediamine (EDA), triethylamine (TEA), trimethylamine, tripropylamine, diethylethanolamine, hexamethylenetetramine (hexamine), lithium carbonate, and any mixture thereof.

[0033] The first reaction mixture can include about 1 wt% to about 30 wt% of the first catalyst, based on the combined weight of the liquid medium, the phenolic monomer, the aldehyde monomer, and the first catalyst. For example, the first reaction mixture can include from about 0.1 wt% to about 1 wt%, about 1 wt% to about 2 wt%, about 2 wt% to about 3 wt%, about 3 wt% to about 5 wt%, about 5 wt% to about 10 wt%, of the first catalyst based on the weight of the phenolic monomer. In another example, the first reaction mixture can include about 0.05 wt%, about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, about 4 wt%, about 4.5 wt%, or about 5 wt% to about 7 wt%, about 10 wt%, about 13 wt%, about 15 wt%, about 17 wt%, about 20 wt%, about 23 wt%, about 25 wt%, about 27 wt%, or about 30 wt%, of the first catalyst based on the weight of the phenolic monomer.

[0034] The molar ratio of the phenolic monomer to first catalyst can be about 1 : 1 to about 400: 1. For example, the molar ratio of the phenolic monomer to first catalyst can be about 1 : 1, about 5: 1, about 10: 1, or about 15: 1 to about 45: 1, about 50: 1, about 60: 1, about 80: 1, about 100: 1, about 125: 1, about 150: 1, about 175: 1, about 200: 1, about 225: 1, about 250: 1, about 275: 1, about 300: 1, about 325 : 1, or about 350: 1. In another example, the molar ratio of the phenolic monomer to first catalyst can be about 1 : 1, about 3 : 1, about 5: 1, about 8: 1, about 10: 1, about 12: 1, or about 15: 1 to about 20: 1, about 25: 1, about 20: 1, about 37: 1, about 40: 1, about 43 : 1, about 45: 1, or about 49: 1. In another example, the molar ratio of the phenolic monomer to first catalyst can be less than 200: 1, less than 150: 1, less than 125: 1, less than 100: 1, less than 75: 1, less than 60: 1, less than 50: 1, less than 49: 1, less than 47: 1, less than 45: 1, less than 43 : 1, less than 40: 1, less than 37: 1, or less than 35: 1.

[0035] The phenolic monomer and the aldehyde monomer can be heated at a temperature of about 20°C to about 300°C to produce the prepolymer. For example, the phenolic monomer and aldehyde monomer can be can be heated at a temperature of about 20°C, about 30°C, about 40°C, about 50°C, or about 60°C to produce the prepolymer. In another example, the phenolic monomer and aldehyde monomer can be heated at a temperature of about 40°C to about 60°C, about 60°C to about 80°C, or about 80°C to about 100°C to produce a prepolymer. In another example, the phenolic monomer and aldehyde monomer can be heated at a temperature form a low of about 20°C, about 40°C, about 60°C, about 80°C, or about 90°C to a high of about 95°C, about 100°C, about 125°C, 150°C, about 175°C, about 200°C, about 225°C, about 250°C, about 275°C, or about 300°C to produce a prepolymer.

[0036] The first reaction mixture can be reacted under a wide range of pH values. For example, the first reaction mixture can be at a pH from about 1, about 2, or about 3 to about 7, about 8, about 9, about 10, about 11, or about 12. In some examples, the first reaction mixture can be at acidic conditions. For example, the pH of the first reaction mixture can be less than 7, less than 6.5, less than 6, less than 5.5, less than about 5, less than 4.5, or less than 4. In another example, the pH of the first reaction mixture can be from about 1 to about 6.5, about 1.5 to about 5.5, about 2 to about 5, about 1.5 to about 4.5, about 1 to about 4, about 2 to about 4, about 1 to about 3.5, or about 2 to about 4.5.

[0037] The prepolymer can have a molar ratio of the one or more phenolic monomers to the one or more aldehyde monomers from about 0.1 : 1 to about 1.5: 1. For example, the molar ratio of the one or more phenolic monomers to the one or more aldehyde monomers can be about 0.2: 1 to about 1.4: 1, about 0.8: 1 to about 1.3 : 1, about 0.2: 1 to about 0.9: 1, about 0.3 : 1 to about 0.8: 1, about 0.4: 1 to about 0.8: 1, about 0.4: 1 to about 0.7: 1, or about 0.4: 1 to about 0.6: 1. In at least one example, the molar ratio of the one or more phenolic monomers to the one or more aldehyde monomers can be about 0.4: 1, about 0.5: 1, about 0.6: 1, about 0.7: 1, about 0.8: 1, about 0.9: 1, or about 1 : 1.

[0038] The prepolymer can have a weight average molecular weight (Mw) from about 200, to about 2000. In one or more examples, the prepolymer can have a weight average molecular weight (Mw) from about 200, about 300, or about 400 to about 1,000, or about 2,000. In another example, the prepolymer can have a weight average molecular weight of about 250 to about 450, about 450 to about 550, about 1,550 to about 2,000. In another example, the prepolymer can have a weight average molecular weight of about 175 to about 800, about 700 to about 2,000, about 1, 100 to about 2,000, about 230 to about 550, about 425 to about 875, or about 475 to about 775. In another example, the prepolymer can have a weight average molecular weight of less than 2,000, less than 1000, less than 500, less than 400, less than 300 or less than 250. The molecular weight of the prepolymer can be determined by Gel Permeation Chromatography (GPC) method.

[0039] The prepolymer can include free aldehyde, i.e., non-reacted aldehyde monomer, in an amount of about 0 wt% to about 20 wt%, based on the weight of the prepolymer. For example, the prepolymer can include about 0.1 wt%, about 1 wt%, about 3 wt%, about 5 wt%, about 7 wt%, or about 9 wt% to a high of about 11 wt%, about 13 wt%, about 15 wt%, about 17 wt%, or about 20 wt% of free aldehyde monomer, based on the weight of the prepolymer. In another example, the prepolymer include about 0 wt%, about 0.5 wt%, about 1 wt%, or about 2 wt% to a high of about 3 wt%, about 5 wt%, or about 6 wt% of free aldehyde monomer, based on the weight of the prepolymer. In another example, the prepolymer can include free formaldehyde from about 0 to about 0.8 wt%, about 1 wt% to 2.5 wt%, about 3.2 wt% to about 4.3 wt%, or about 5 wt% to about 5.7 wt%, based on the weight of the prepolymer. In still another example, the prepolymer can include less than 20 wt%, less than 17 wt%, less than 15 wt%, less than 13 wt%, less than 11 wt%, less than 9 wt%, less than 7 wt%, less than 5 wt%, less than 3 wt%, less than 1 wt%, less than 0.7 wt%, less than 0.5 wt%, less than 0.3 wt%, less than 0.1 wt%, or less than 0.05 wt% of the free formaldehyde based on the weight of the prepolymer.

[0040] The prepolymer can include free phenol from about 0 wt% to about 20 wt%, based on the weight of the prepolymer. For example, the prepolymer can include free phenol of about 0.1 wt%, about 1 wt%, about 3 wt%, about 5 wt%, about 7 wt%, or about 9 wt% to about 1 1 wt%, about 13 wt%, about 15 wt%, about 17 wt%, or about 20 wt% based on the weight of the prepolymer. In another example, the prepolymer can include free phenol from about 0 wt%, about 0.5 wt%, about 2 wt%, or about 4 wt% to about 8 wt%, about 10 wt%, or about 12 wt%, based on the weight of the prepolymer. In another example, the prepolymer can include free phenol form about 0 to about 1.5 wt%, about 2 wt% to 4.5 wt%, about 5.2 wt% to about 6.3 wt%, about 7.2 wt% to about 8.8 wt% or about 9 wt% to about 10.7 wt%, based on the weight of the prepolymer. In still another example, the prepolymer can include free phenol of less than 20 wt%, less than 17 wt%, less than 15 wt%, less than 13 wt%, less than 11 wt%, less than 9 wt%, less than 7 wt%, less than 5 wt%, less than 3 wt%, less than 1 wt%, less than 0.7 wt%, less than 0.5 wt%, less than 0.3 wt%, less than 0.1 wt%, or less than 0.05 wt% based on the weight of the prepolymer. [0041] The prepolymer can have a refractive index from about 1.1000 to about 1.5500. In one or more examples, the prepolymer can have a refractive index from about 1.1000, about 1.1500, about 1.2000, about 1.2500, about 1.3000, or about 1.3200 to about 1.4000, about 1.4500, about 1.4800, about 1.5000, or about 1.5500. In another example, the polymerization of the monomer mixture to produce the prepolymer can be carried out to a refractive index of about 1.3500 to about 1.4500, about 1.3800 to about 1.4400, about 1.3900 to about 1.4350, of about 1.3900 to about 1.4500. A Bellingham + Stanley Ltd RFM 330 refractometer can be used to determine the refractive index of the prepolymers. The refractive index measurement procedure is as follows. Water at a temperature of about 25.0°C is circulated into the refractometer 1 hr. before each refractive index (RI) measurement. The cleanliness of the prism is checked. If the RI reading of distilled water left from the previous RI measurement is not 1.3325+/-0.0001, the prism and presser were cleaned with distilled water, methanol, isopropyl alcohol, or other suitable solvent, and the prism is then refilled with distilled water. The presser is immediately closed and the RI measurement taken. This step is repeated if necessary until the RI reading of distilled water reads 1.3325±0.0001. The distilled water on the prism and the presser is wiped off after the refractometer is calibrated. The presser of the refractometer is lifted and the about 0.5 mL to about 1.0 ml of the sample transferred to the prism with a plastic pipette. For an RI measurement, there must be sufficient sample transferred to the prism such that the entire prism area is covered with the sample. The sample is gently stirred in the prism with the pipette tip to break the surface tension. The presser is then closed and the RI measurement taken. The temperature displayed by the refractometer is at 25°C +/- ±0.1°C. The preceding procedure is repeated until two successive readings equal to or within 0.0001 RI units are acquired and the average of those two successive readings are the RI values reported.

[0042] In one example, at least a portion of the prepolymer or the first reaction mixture can be mixed, blended, stirred, or otherwise combined with one or more second catalysts to produce the second reaction mixture. In another example, at least a portion of the prepolymer or the first reaction mixture can be mixed, blended, stirred, or otherwise combined with one or more second catalysts and one or more carrier fluids to produce the second reaction mixture. The second reaction mixture can be a slurry, suspension, dispersion and/or emulsion. In one or more examples, at least portion of the prepolymer can be added to the carrier fluid, the carrier fluid can be added to the prepolymer, or the prepolymer and the carrier fluid can be simultaneously combined with one another to form the slurry, dispersion, suspension or emulsion. [0043] The second catalyst can also be referred to as an initiator, a reducer, and/or an accelerator. In some examples, the second catalyst can be unconsumed by the polymerization reaction. In some examples, the second catalyst can be partially consumed by the polymerization reaction. In other examples, the second catalyst can be consumed by the polymerization reaction. For example, consumption or at least partial consumption of the second catalyst can include the second catalyst reacting with the phenolic monomer, the aldehyde monomer, the first catalyst, the prepolymer, itself, or any combination thereof. The second catalyst can be or include one or more carboxylic acids, one or more anhydrides, one or more dihydroxybenzenes, or any mixture thereof. Illustrative second catalysts can include, but are not limited to, maleic anhydride, maleic acid, phthalic anhydride, phthalic acid, resorcinol, catechol, hydroquinone, bisphenol A, bisphenol F, or any mixture thereof. For example, the second catalyst can be or include maleic anhydride, resorcinol, or a mixture of maleic anhydride and resorcinol. The carboxylic acid can be or include a monocarboxylic acids, a dicarboxylic acids, a tricarboxylic acids, a tetracarboxylic acids, a pentacarboxylic acids, a hexacarboxylic acids, any polycarboxylic acids, or a mixture thereof.

[0044] It should be noted that, as discussed above, dihydroxybenzene can be or make up at least a portion of the phenolic monomer component. As such, one or more dihydroxybenzenes can be or make up at least a portion of the phenolic monomer component and/or can be or make up at least a portion of the second catalyst. If the phenolic monomer and the second catalyst both include a dihydroxybenzene, the dihydroxybenzene in the phenolic monomer can be referred to as a "first dihydroxybenzene" and the dihydroxybenzene in the second catalyst can be referred to as a "second dihydroxybenzene." When a dihydroxybenzene is used as the second catalyst, the dihydroxybenzene making up the second catalyst can be added to the prepolymer formed by reacting the first reaction mixture that includes the phenolic monomer, which may or may not include the first dihydroxybenzene, the aldehyde monomer, and the first catalyst. It should also be noted that the phenolic monomer and the second catalyst can both include the same dihydroxybenzene compound. In at least one example, the phenolic monomer can be or include resorcinol and the second catalyst can also be or include resorcinol.

[0045] The second reaction mixture can include greater than 30 wt% of the second catalyst based on the weight of the phenolic monomer. For example, the second reaction mixture can include greater than 30.5 wt%, greater than 3 lwt%, greater than 32 wt%, greater than 33 wt%, greater than 34 wt%, greater than 35 wt% greater than 36 wt%, greater than 37 wt% , greater than 38 wt%, greater than 39 wt%, greater than 40 wt%, greater than 50 wt% , greater than 60 wt%, greater than 70 wt%, greater than 80 wt%, greater than 90 wt% , greater than 100 wt%, greater than 1 10 wt%, greater than 120 wt% , greater than 130 wt%, greater than 140 wt%, or greater than 190 wt%, of the second catalyst based on the weight of the phenolic monomer. For example, the second reaction mixture can include from about 30 wt% to about 35 wt%, about 35 wt% to about 40 wt%, about 40 wt% to about 45 wt%, about 45 wt% to about 50 wt%, about 50 wt% to about 60 wt%, about 60 wt% to about 70 wt%, about 70 wt% to about 80 wt%, about 80 wt% to about 90 wt%, about 90 wt% to about 100 wt%, about 100 wt% to about 1 10 wt%, about 1 10 wt% to about 120 wt%, about 120 wt% to about 130 wt%, about 130 wt% to about 140 wt%, about 140 wt% to about 150 wt%, about 150 wt% to about 160 wt%, about 160 wt% to about 170 wt%, about 170 wt% to about 180 wt%, about 180 wt% to about 190 wt%, about 190 wt% to about 200 wt% , of the second catalyst based on the weight of the phenolic monomer.

[0046] The molar ratio of the phenolic monomer to second catalyst can be about 0.001 : 1 to about 1 : 1. For example, the molar ratio of the phenolic monomer to the second catalyst can be about 0.001 : 1, about 0.002: 1, about 0.003 : 1, about 0.004: 1, about 0.005 : 1, about 0.006: 1, about 0.007: 1, about 0.008: 1, about 0.009: 1, about 0.01 : 1, about 0.02: 1, about 0.03 : 1, about 0.04: 1, about 0.05 : 1, about 0.06: 1, about 0.07: 1, about 0.08: 1, about 0.09: 1, about 0.1 : 1, about 0.2: 1, about 0.3 : 1, about 0.4: 1, about 0.5 : 1, about 0.6: 1, about 0.7: 1, about 0.8: 1, about 0.9: 1 or about 0.95 : 1.

[0047] In one or more examples, the polymer gel and /or the polymer particles in gel form can be produced in less than 25 minutes by polymerizing the prepolymer at a temperature of at least 95°C, as measured according to ASTM D2471-99. For example, the polymer gel and /or the polymer particles in gel form can be produced in less than 25 minutes, less than 24 minutes, less than 23 minutes, less than 22 minutes, less than 21 minutes, less than 20 minutes, less than 19 minutes, less than 18 minutes, less than 17 minutes, less than 16 minutes, less than 15 minutes, less than 14 minutes, less than 13 minutes, less than 12 minutes, less than 1 1 minutes, less than 10 minutes, less than 9 minutes, less than 8 minutes, less than 7 minutes, less than 6 minutes, less than 5 minutes, less than 4 minutes, less than 3 minutes, less than 2.5 minutes, less than 2 minutes, less than 1.5 minutes, or less than 1 minute. In one example, the prepolymer can be polymerized by heating the prepolymer at a temperature of at least 95°C, at least 100°C at least 105°C at least 1 10°C at least 1 15°C at least 120°C at least 125°C at least 130°C at least 135°C at least 140°C at least 145°C, or at least 150°C to produce the polymer gel and/or polymer particles in gel form in less than 25 minutes. The time to form the polymer gel or polymer particles in gel form can be measured according to ASTM D2471-99.

[0048] In one or more examples, the second reaction mixture can include a carrier fluid. The carrier fluid can be or include one or more hydrocarbons, water, or a combination or mixture thereof. Illustrative carrier fluids can be or include, but are not limited to, paraffinic oils, naphthenic oils, aromatic oils, or any mixture thereof. Illustrative paraffinic hydrocarbons can be or include mineral oils or any thereof. Suitable mineral oils include one or more alkanes having from about 15 to about 40 carbon atoms. Illustrative naphthenic oils can be hydrocarbons based on cycloalkanes. Illustrative cycloalkanes can include, but are not limited to cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, or any combination or mixture thereof. Another suitable carrier fluid can be or include one or more plant based or plant derived oils. Illustrative plant based or plant derived oils can include, but are not limited to, such as linseed (flaxseed) oil, castor oil, lung oil, soybean oil, cottonseed oil, olive oil, canola oil, corn oil, sunflower seed oil, peanut oil, coconut oil, safflower oil, palm oil, vegetable oil, or any combination or mixture thereof. Suitable commercially available vegetable oils can include, but are not limited to, those sold under the tradename WESSON® and sold by CONAGRA FOODS®, such as the vegetable oil, canola oil, corn oil, blended oils, and the like. Another suitable carrier fluid can be or include one or more chlorinated hydrocarbons. Illustrative chlorinated hydrocarbons can include, but are not limited to, carbon tetrachloride, chloroform, methylene chloride, or any combination or mixture thereof. Any type of water can be used as the carrier fluid or to make-up at least a portion of the carrier fluid. For example, the water can be distilled water, deionized water, or a combination or mixture thereof. In another example, the water can be tap water.

[0049] The use of a carrier fluid that contains or includes water can reduce the cost associated with the production of the polymer particles in gel form as compared to the use of hydrocarbons. The use of a carrier fluid that contains or includes water can also allow for an increased concentration of the monomer component relative to the carrier fluid as compared to a carrier fluid that contains one or more hydrocarbons and is free or substantially free of water, e.g., less than 5 wt% water. In other words, a carrier fluid that is or includes a majority of water, e.g., greater than about 50 wt% water, can allow for a more concentrated second mixture to be formed as compared to when the carrier fluid is or includes a majority of non-water fluid(s), e.g., greater than about 50 wt% hydrocarbons. The use of a carrier fluid that is or includes water may also at least partially remove any residual carrier fluid composed of one or more hydrocarbons.

[0050] The carrier fluid can have a boiling point of about 40°C or more, about 50°C or more, about 60°C or more, about 70°C or more, about 80°C or more, about 90°C or more, about 100°C or more, about 110°C or more, about 120°C or more, about 130°C or more, about 140°C or more, or about 150°C or more. The carrier fluid can have a flash point greater than about - 25°C, greater than about -20°C, greater than about -10°C, greater than about 0°C, greater than about 10°C, greater than about 20°C, greater than about 30°C, greater than about 40°C, greater than about 50°C, or greater than about 60°C.

[0051] In some examples, the carrier fluid can be free or substantially free of cycloalkanes, e.g., cyclohexane, cycloheptane, cyclooctane, and the like. For example, the carrier fluid can contain less than about 1 wt% cyclohexane, based on the total weight of the carrier fluid. As such, the use of cyclohexane as a carrier fluid can be avoided.

[0052] In one or more examples, the prepolymer in the second reaction mixture can be polymerized by heating to a temperature of about 20°C to about 300°C. In one or more examples, the prepolymer in the second reaction mixture can be polymerized by heating to a temperature of about 20°C, about 30°C, about 40°C, about 50°C, about 70°C, about 80°C, or about 90°C to a high of about 95°C, about 100°C, about 110°C, about 125°C, 150°C, about 175°C, about 200°C, about 225°C, about 250°C, about 275°C, or about 300°C. For example, the temperature of the second reaction mixture including the prepolymer can be maintained, e.g., from about 80°C to about 99°C till polymerization is complete. In another example, the temperature of the second reaction mixture including the prepolymer can be maintained at a temperature of about 80°C or more, about 83°C or more, about 85°C or more, about 87°C or more, about 90°C or more, about 93°C or more, about 95°C or more, about 97°C or more, about 98°C or more, about 99°C or more, about 100°C or more, about 103°C or more, about 105°C or more, about 107°C or more, about 110°C or more, about 112°C or more, or about 115°C or more until the polymerization reaches a desired degree or level of polymerization.. The polymerization of the prepolymer in the second reaction mixture can be carried out under a wide range of pH values. For example, the polymerization can be carried out at a pH from about 1, about 2, or about 3 to about 7, about 8, about 9, about 10, about 11, or about 12. In one or more examples, polymerization of the prepolymer can be carried out under acidic conditions. For example, the pH of the reaction mixture or at least the monomer component can be less than about 7, less than about 6.5, less than about 6, less than about 5.5, less than about 5, less than about 4.5, or less than about 4. In another example, the pH of the second reaction mixture can be from about 1 to about 6.5, about 1.5 to about 5.5, about 2 to about 5, about 1.5 to about 4.5, about 1 to about 4, about 2 to about 4, about 1 to about 3.5, or about 2 to about 4.5.

[0053] In one or more examples, the second reaction mixture can be a slurry, suspension, dispersion and/or emulsion and can be agitated to improve and/or maintain a homogeneous or substantially homogenous distribution of the second reaction mixture within or in the carrier fluid (suspension and inverse emulsion) or a homogeneous or substantially homogenous distribution of the carrier fluid within or in the reaction mixture (suspension and normal emulsion). The components of the slurry, dispersion, suspension and/or emulsion can be combined within one or more mixers. The mixer can be or include any device, system, or combination of device(s) and/or system(s) capable of batch, intermittent, and/or continuous mixing, blending, contacting, or the otherwise combining of two or more components.

Illustrative mixers can include, but are not limited to, mechanical mixer agitation, ejectors, static mixers, mechanical/power mixers, shear mixers, sonic mixers, vibration mixing, e.g., movement of the mixer itself, or any combination thereof. The mixer can include one or more heating jackets, heating coils, internal heating elements, cooling jackets, cooling coils, internal cooling elements, or the like, to regulate the temperature therein. The mixer can be an open vessel or a closed vessel. The components of the suspension and/or emulsion can be combined within the mixer under a vacuum, at atmospheric pressure, or at pressures greater than atmospheric pressure. The components of the second reaction mixture, can be combined within the mixer and heated to a temperature from about 1°C to about 300°C. The mixer can be capable of producing a homogeneous suspension and/or emulsion. In other words, the mixer can produce a slurry, dispersion, suspension and/or emulsion in which the distribution of the monomer component is substantially the same throughout the carrier fluid. The particular process or combination of methods used to agitate the dispersion, slurry, suspension and/or emulsion can be used, at least in part, as one variable that can be controlled or adjusted to influence the size and/or morphology of the polymer gel and/or polymer particles in gel form.

For example, if a stirring paddle or blade agitates the suspension and/or emulsion by rotation within the suspension and/or emulsion, the speed at which the stirring paddle or blade rotates can influence the size of the polymer particles in gel form. The particular shape or configuration of the stirring paddle or blade can also influence the size of the polymer particles in gel form.

[0054] Once the slurry, dispersion, suspension and/or emulsion forms the phenolic monomer and the aldehyde monomer and/or the prepolymer can be polymerized to produce the polymer gel and /or polymer particles in gel form. In one or more examples, the phenolic monomer, the aldehyde monomer, and/or prepolymer can form small droplets or micelles in the suspension and/or emulsion. The phenolic monomer, aldehyde monomer, and/or the prepolymer contained within the droplets or micelles can polymerize to produce the polymer particles in gel form. The liquid that can at least partially fill any pores or voids in the polymer gel particles can be present in the reaction mixture and/or formed during polymerization of the monomer component.

[0055] In one or more examples, the phenolic monomer and aldehyde monomer, the carrier fluid, and/or the second catalyst can be in the gaseous phase. In another example, the phenolic monomer and aldehyde monomer, and the carrier fluid can be in the gaseous phase and the catalyst can be in the solid and/or liquid phase. Accordingly, in one or more examples, the reaction mixture or at least one or more components of the reaction mixture can be introduced to the reactor in gas phase. In one or more embodiments, the reaction mixture or at least one or more of the components thereof can be in a liquid phase. In one or more embodiments, the reaction mixture or at least one or more monomer thereof can be in a solid phase. In one or more examples, polymerization in the second reaction mixture, when utilizing liquid components, can be carried out at a pressure from about 101 kPa to about 5,500 kPa. In one or more examples, the polymerization can also be carried out at a temperature from a low of about 0°C, about 20°C, about 40°C, or about 50°C to a high of about 70°C, about 80°C, about 90°C, about 100°C, about 120°C, or about 150°C.

[0056] In one or more examples, the molar ratio of the one or more phenolic monomers to the one or more aldehyde monomers of the polymer gel and /or polymer particles in gel form can be from a low of about 0.1 : 1 to a high of about 1.5: 1. For example, the molar ratio of the one or more phenolic monomers to the one or more aldehyde monomers can be about 0.2: 1 to about 1.4: 1, about 0.8: 1 to about 1.3 : 1, about 0.2: 1 to about 0.9: 1, about 0.3 : 1 to about 0.8: 1, about 0.4: 1 to about 0.8: 1, about 0.4: 1 to about 0.7: 1, or about 0.4: 1 to about 0.6: 1. In at least one example, the molar ratio of the one or more phenolic monomer to the one or more aldehyde monomer can be about 0.4: 1, about 0.5: 1, about 0.6: 1, about 0.7: 1, about 0.8: 1, about 0.9: 1, or about 1 : 1.

[0057] The polymer particles in gel form can have an average cross-sectional length of about

0.1 mm to about 10 mm. In one or more examples, the polymer particles in gel form can have an average cross-sectional length of about 0.1 mm or more, about 0. 5 mm or more, about 1 mm or more, about 1.5 mm or more, about 2 mm or more, about 2.5 mm or more, about 3 mm or more, about 3.5 mm or more, about 4 mm or more, about 4.5 mm or more, about 5 mm or more, about 5.5 mm or more, or about 6 mm or more. The polymer particles in gel form can have a particle size distribution, i.e., the average cross-sectional length for any two polymer particles in gel form can vary. For example, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, or about 100% of the polymer particles in gel form can have an average cross-sectional length greater than or equal to 1 mm. In another example, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 95 %, or about 100% of the polymer particles in gel form can have an average cross-sectional length greater than or equal to 1.1 mm. In another example, about 10%, about 20%, about 30%, about 40%, about 50%, about

60%, about 70%, about 80%, about 90%, about 95%, or about 100% of the polymer particles in gel form can have an average cross-sectional length greater than or equal to 1.2 mm. In another example, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about

70%), about 80%), about 90%, about 95%, or about 100% of the polymer particles in gel form can have an average cross-sectional length greater than or equal to 1.3 mm. In another example, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%), about 95%, or about 100% of the polymer particles in gel form can have an average cross-sectional length greater than or equal to 1.5 mm. In another example, about 10%, about

20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about

95%), or about 100%> of the polymer particles in gel form can have an average cross-sectional length greater than or equal to 1.7 mm. In another example, about 10%, about 20%, about

30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, or about 100%) of the polymer particles in gel form can have an average cross-sectional length greater than or equal to 2 mm. In still another example, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, or about

100%) of the polymer particles in gel form can have an average cross-sectional length greater than or equal to about 1 mm, about 1.2 mm, about 1.4 mm, about 1.6 mm, about 1.8 mm, about 2.1 mm, about 2.3 mm, or about 2.5 mm. In yet another example, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, or about 100%) of the polymer particles in gel form have an average cross-sectional length greater than or equal to about 1 mm, about 1.5 mm, about 2 mm, about 2.5 mm, about 3 mm, about 3.5 mm, about 4 mm, about 4.5 mm, about 5 mm, or about 5.5 mm.

[0058] The polymer particles in gel form can have a surface area from about 50 m²/g to about 1,300 m²/g. In one or more examples, the polymer particles in gel form can have a surface area of about 50 m²/g, about 100 m²/g, about 200 m²/g, about 400 m²/g, or about 500 m²/g to about 800 m²/g, about 1,100 m²/g, about 1,400 m²/g, about 1,700 m²/g, or about 2,000 m²/g. For example, the surface area of the polymer particles in gel form can be from about 75m²/g to about 700 m²/g, about 350 m²/g to about 1,000 m²/g, about 850 m²/g to about 1,750 m²/g, or about 600 m²/g to about 1,300 m²/g.

[0059] The polymer particles in gel form can have a pore size from about 0.2 nm to 300 nm. In one or more examples, the polymer particles in gel form can have a pore size from about 0.2 nm, about 0.5 nm, about 1 nm, about 5 nm, or about 10 nm to about 100 nm, about 200 nm, about 300 nm, about 400 nm, or about 500 nm. For example, the pore size of the polymer particles in gel form can be from about 3 nm to about 75 nm, about 15 nm to about 150 nm, about 40 nm to about 450 nm, or about 20 nm to about 300 nm.

[0060] The polymer particles in gel form can also be referred to as being microporous, i.e., having an average pore size less than or equal to 2 nm, mesoporous, i.e., having an average pore size of about 2 nm to about 50 nm, or macroporous, i.e., having an average pore size of greater than 50 nm). The polymer particles can have only a microporous pore size distribution, only a mesoporous pore size distribution, or only a macroporous pore size distribution. In another example, the polymer particles can have a combination of micropores, mesopores, and/or macropores.

[0061] In some examples, the polymer particles in gel form can have a monomodal pore size distribution, a bimodal pore size distribution, or a multi-modal pore size distribution. In another example, the polymer particles can have only a monomodal pore size distribution, a bimodal pore size distribution, or a multi-modal pore size distribution.

[0062] The polymer gel and/or polymer particles in gel form can have a pore volume from of about 0.05 cm³/g to about 4 cm³/g. In one or more examples, the polymer particles in gel form can have a pore volume of about 0.05 cm³/g, about 0.1 cm³/g, about 0.5 cm³/g, about 1 cm³/g, or about 1.5 cm³/g to about 2 cm³/g, about 2.5 cm³/g, about 3 cm³/g, about 3.5 cm³/g, or about 4 cm³/g. For example, the surface area of the polymer particles in gel form can be from about 0.05cm³/g to about 1 cm³/g, about 0.7 cm³/g to about 3.5 cm³/g, about 0.5 cm³/g to about 3 cm³/g, or about 2.5 cm³/g to about 4 cm³/g.

[0063] The polymer gel can be a monolithic body or particles. The monolith can take the form of the reaction vessel the polymer gel is made in.

[0064] The residual heat of the polymer gel (monolith or particles) can be less than 15 J/g, less than 14 J/g, less than 13 J/g, less than 12 J/g, less than 11 J/g, less than 10 J/g, less than 9 J/g, less than 8 J/g, less than 7 J/g, less than 6 J/g, less than 5 J/g, less than 4 J/g, less than 3 J/g, less than 2 J/g, as measured by differential scanning calorimetry (DSC).

[0065] In one or more examples, the polymer gel can be further processed to produce a thermoset polymer. In one example, the polymer gel can be further processed by heating the polymer gel at a temperature of about 2^5oC to about 15^0oC to produce a thermoset polymer. In another example, the polymer gel can be further processed by contacting the polymer gel with a fluid comprising water, alcohol or a mixture thereof to produce a washed polymer gel; and drying the washed polymer gel to produce a dried polymer gel. The drying can include heating, vacuum drying, freeze drying, or a combination thereof. In another example, the polymer gel can be further processed by heating the polymer gel at a temperature of about 60^0oC to about l,80^0oC for about 30 seconds to about 10 hours to produce a porous carbonaceous material.

[0066] In one or more examples, the polymer particles in gel form can be further processed to produce a thermoset polymer. For example, the polymer particles in gel form can be heated at a temperature of about 25°C to about 150°C to produce a thermoset polymer. In another example, the polymer particles in gel form can be contacted with a fluid that can include, but is not limited to, water, alcohol, or a mixture thereof to produce washed polymer particles in gel form. The washed polymer particles in gel form can be dried to produce dried polymer particles. The polymer particles in gel form and/or the washed polymer particles in gel form can be heated, subjected to vacuum drying, subjected to freeze drying, or a combination thereof to produce the dried polymer particles. In another example, the polymer particles in gel form can be heated at a temperature of about 600°C to about 1,800°C for about 30 seconds to about 10 hours to produce a porous carbonaceous material. [0067] In one specific example, a process for making a porous carbonaceous material from a polymer gel can include making a prepolymer from a first reaction mixture that includes phenol, resorcinol, formaldehyde, and a first catalyst. The first catalyst can include one or more amines and/or one or more metal catalyst. Illustrative first catalysts can include, but are not limited to ammonia, dimethylethanolamine (DMEA), ethylenediamine (EDA), triethylamine (TEA), hexamethylenetetramine (hexamine), and lithium carbonate, and any mixture thereof. The prepolymer can be combined with a second catalyst to produce a second reaction mixture. The second catalyst can be or include one or more carboxylic acids, anhydrides, resorcinol, or any mixture thereof. As discussed above, illustrative second catalysts can include, but are not limited to maleic anhydride, maleic acid, phthalic anhydride, phthalic acid, resorcinol, any combination thereof, or any mixture thereof. For example, the second catalyst can include maleic anhydride, resorcinol, or a mixture thereof. The second reaction mixture can include greater than 30 wt% of the second catalyst based on a weight of the phenolic monomer. The prepolymer can be polymerized to produce the polymer gel in less than 25 minutes, at a temperature of at least about 95°C, as measured according to ASTM- D2471-99. The molar ratio of the phenolic monomer to the second catalyst can be about 0.001 : 1 to about 1 : 1. The prepolymers can be polymerized in a reactor to form a polymer gel. The polymer gel form can be recovered from the reactor. The polymer gel can be heated at a temperature of about 600°C to about 1,800°C for about 30 seconds to about 10 hours to produce a porous carbonaceous material.

[0068] In another specific example, a process for making a porous carbonaceous material from polymer particles in gel form can include making a prepolymer from a first reaction mixture that includes phenol, resorcinol, formaldehyde, and a first catalyst. The first catalyst can include one or more amines and/or one or more metal catalyst. Illustrative first catalysts can include, but are not limited to ammonia, dimethylethanolamine (DMEA), ethylenediamine

(EDA), triethylamine (TEA), hexamethylenetetramine (hexamine), and lithium carbonate, and any mixture thereof. The prepolymer can be combined with a carrier fluid and a second catalyst to produce a second reaction mixture. The carrier fluid can include vegetable oil, mineral oil, or mixtures thereof. The second reaction mixture can be a suspension and/or emulsion. The second catalyst can be or include one or more carboxylic acids, anhydrides, resorcinol, or any mixture thereof. As discussed above, illustrative second catalysts can include, but are not limited to maleic anhydride, maleic acid, phthalic anhydride, phthalic acid, resorcinol, any combination thereof, or any mixture thereof. For example, the second catalyst can include maleic anhydride, resorcinol, or a mixture thereof. The second reaction mixture can include greater than 30 wt% of the second catalyst based on a weight of the phenolic monomer. The prepolymer can be polymerized to produce the polymer particles in gel form in less than 25 minutes, at a temperature of at least about 95°C, as measured according to ASTM- D2471-99. The molar ratio of the phenolic monomer to the second catalyst can be about 0.001 : 1 to about 1 : 1. The prepolymers in the suspension and/or emulsion can be polymerized in a reactor to form polymer particles in gel form. The polymer particles in gel form can be recovered from the reactor. The polymer particles in gel form can be heated at a temperature of about 600°C to about 1,800°C for about 30 seconds to about 10 hours to produce a porous carbonaceous material.

[0069] In one or more examples, the liquid and/or carrier fluid contained in and/or on the polymer particles in gel form can be replaced with a more volatile solvent via solvent exchange. For example, the polymer particles in gel form can be contacted with a hydrocarbon solvent, e.g., acetone, which can remove at least a portion of the liquid medium and/or the carrier fluid and with the hydrocarbon solvent. The hydrocarbon solvent can then be more readily removed from the polymer particles in gel form to provide substantially dry polymer particles via heating, supercritical extraction, air drying, freeze drying, and the like. However, the polymer particles in gel form that contain the liquid and/or carrier fluid can also be dried via supercritical, air, or freeze drying.

[0070] The process of heating a polymer gel or polymer particles in gel form to produce a porous carbonaceous material can also be termed as a "pyrolysis process" or a "carbonization process". The resulting carbonized or pyrolyzed material contain primarily carbon. Any pyrolyzation or carbonization process can be used. In one example, the polymer gel or polymer particles in gel form can be placed into a rotary kiln and heated therein. The pyrolysis process can be carried out under an inert atmospheres, e.g., a nitrogen, argon, or other inert gas or gas mixture. Pyrolysis processes are well known to those of skill in the art. The duration of the pyrolysis, i.e., the period of time during which the polymer particles are maintained at the elevated temperature can be from about 30 seconds to about 10 hours, about 1 minute to about 5 hours, about 5 minutes to about 2 hours, about 10 minutes to about 1 hour, or about 20 minutes to about 45 minutes. The pyrolysis dwell temperature can be from about 600°C to about 1,800°C, about 600°C to about 1,200°C, or about 650°C to about 1,100°C. [0071] In some examples, the porous carbonaceous material can be activated. Activating the porous carbonaceous material can include any activation process or combination of activation processes known to those skilled in the art. The activation time and/or activation temperature can affect the performance of the resulting activated carbon material, as well as the manufacturing cost thereof. For example, increasing the activation temperature and the activation dwell time can yield higher activation percentage of the carbonaceous materials, but can also correspond to the removal of more material compared to lower temperatures and shorter dwell times. As such, higher activation can increase performance of the final activated carbon, but it can also increase the cost of the process by reducing the overall carbonized product.

[0072] The porous carbonaceous materials can be activated by contacting the materials with an activating agent. Illustrative activating agents can be or include gases such as carbon dioxide, steam, oxygen, or any combination or mixture thereof. Other activating agents can include other compounds or chemicals. The activation process can be from about 1 minute to about 2 days, about 5 minutes to about 1 day, about 1 minute to about 18 hours, about 1 minute to about 12 hours, about 5 minutes to about 8 hours, about 1 minute to about 10 minutes, or about 1 hour to about 5 hours.

[0073] In one example of an activation process, the porous carbonaceous material can be weighed and placed in a rotary kiln and an automated gas control manifold and controller can be set to ramp rate of about 20°C per minute. Carbon dioxide can be introduced to the kiln environment for a period of time once the proper activation temperature has been reached. After activation has occurred, the carbon dioxide can be replaced by nitrogen and the kiln can be cooled down. The recovered activated porous carbonaceous materials can be weighed at the end of the process to assess the level of activation. Other activation processes are well known to those of skill in the art. Suitable activation temperatures can be from about 800°C to about 1,300°C, about 900°C to about 1,050°C, or about 900°C to about 1,000°C.

[0074] Illustrative applications that can use the polymer gel, the polymer particles in gel form, and porous carbonaceous materials derived there from can include, but are not limited to, insulation, energy, e.g., in capacitors, batteries, and fuel cells, medicine, e.g., drug delivery, transportation, e.g., hydrogen or other fuel storage, sensors, sports, catalysts, hazardous waste water treatment, catalyst supports, sorbents, dielectrics, impedance matcher, detectors, filtrations, ion exchange, high-energy physics applications, waste management, such as adsorption of waste fluids and/or waste gases, and the like.

Examples

[0075] In order to provide a better understanding of the foregoing discussion, the following non-limiting examples are offered. Although the examples may be directed to specific embodiment, it is not to be viewed as limiting the invention in any specific respect. All parts, proportions, and percentages are by weight unless otherwise indicated.

[0076] Example I Phenol (about 1,559.7 g) and formaldehyde 50% (about 1,393.5 g) were added to a reactor. The reaction mixture was heated to about 55° C. Triethylamine (about 46.8 g) was added slowly to the reactor over 30 minutes. The reaction mixture was then heated to about 78° C. for about 45 minutes. The reaction mixture was held at about 78°C until the Oswaldt viscosity reached about 60 centistokes. The reaction mixture was cooled to about 55°C and then distilled (under vacuum) to produce a prepolymer solution that had a water content of 13% and a viscosity of 650 centipoise (cP). The resulting prepolymer was cooled to about 25°C and placed into collection bottles. About 3.22 g of resorcinol, about 3.22 grams of maleic anhydride and about 86.02 grams of acetic acid were added to 107.53 g of the prepolymer solution (87% solids). The prepolymer and the catalyst mixture was stored at a temperature of about 5°C overnight. The concentration of the second catalyst (maleic anhydride plus resorcinol) in the second reaction mixture was 9.9 wt%, based on the weight of the phenolic monomer. The concentration of the second catalyst in the second reaction mixture was 3.2 wt% based on the total weight of the second reaction mixture. The second reaction mixture was mixed for 30 minutes at 95°C and then the gel time was measured according to ASTM-2471-99 method. A gel time of 80.55 minutes was recorded. After gel formation, the polymer gel was heated at about 95°C for 4 days to provide a thermoset polymer. Differential Scanning Calorimetry (DSC) was used to measure the residual reaction heat after the curing process and a residual heat of 19 J/g was recorded. The high residual heat was indicative of a slow curing reaction.

Example-II

[0077] Phenol (about 2,973.75 g) and Triethylamine (about 88.5 g) were added to a reactor. The reaction mixture was heated to 80° C. Formaldehyde 50% solution (about 3,971.7 g) was added slowly to the reactor over 30 minutes. This first reaction mixture was held at about 80° C until a viscosity of 60 cP was reached. The product of the first reaction mixture was the prepolymer. The prepolymer had 65% solids and 35% liquids. The prepolymer was cooled to about 25° C and placed into collection bottles and stored in a cold room a 5° C. Next, to about 72.81 g of the prepolymer, about 24.27 g of maleic anhydride, and about 2.91 g of resorcinol were added to provide a second reaction mixture. The concentration of the second catalyst (maleic anhydride plus resorcinol) in the second reaction mixture was 96 wt% based on the weight of the phenolic monomer. The concentration of the second catalyst in the second reaction mixture was 27.2 wt% based on the total weight of the second reaction mixture. The second reaction mixture was mixed for 30 minutes at about 95°C and then the gel time measured according to ASTM-2471-99. Surprisingly and unexpectedly a gel time of only 1.9 minutes was measured. Without wishing to be bound by theory, it is believed that the relatively high concentration of the second catalyst (96 wt% based on the weight of the phenolic monomer) in the second reaction mixture at least contributed to the short gel time. After gel formation, the polymer gel was heated at about 95°C for 2 days to provide a cured thermoset polymer. Differential Scanning Calorimetry (DSC) was also used to measure the residual reaction heat after the curing process and a residual heat of 10 J/g was recorded. The low residual heat was indicative of a fast curing reaction.

[0078] Embodiments of the present disclosure further relate to any one or more of the following paragraphs:

[0079] 1. A process for making a polymer gel, comprising: reacting a first reaction mixture comprising a phenolic monomer, an aldehyde monomer, and a first catalyst to produce a prepolymer; combining a second catalyst with the prepolymer to produce a second reaction mixture, wherein the second reaction mixture comprises greater than 30 wt% of the second catalyst based on a weight of the phenolic monomer; and polymerizing the prepolymer to produce the polymer gel at a temperature of at least about 95°C in less than 25 minutes, as measured according to ASTM- D2471-99.

[0080] 2. A process for making a polymer gel comprising: reacting a first reaction mixture comprising a phenolic monomer and formaldehyde in the presence of a first catalyst to produce a prepolymer, wherein the phenolic monomer comprises phenol, a first dihydroxybenzene, or a mixture thereof; combining a second catalyst with the prepolymer to produce a second reaction mixture, wherein the second reaction mixture comprises greater than 30 wt% of the second catalyst based on a weight of the phenolic monomer; and wherein the second catalyst comprises an anhydride, a second dihydroxybenzene, or a mixture thereof; and polymerizing the prepolymer to produce the polymer gel at a temperature of at least about 95°C in less than 25 minutes, as measured according to ASTM- D2471-99.

[0081] 3. The process according to any one of paragraphs 1 or 2, further comprising, contacting the polymer gel with a fluid comprising water, alcohol or a mixture thereof to produce a washed polymer gel.

[0082] 4. The process according to any one of paragraphs 1 to 3, further comprising, drying the washed polymer gel to produce a dried polymer gel.

[0083] 5. The process according to any one of paragraphs 1 to 4, wherein the drying comprises heating, vacuum drying, freeze drying or a combination thereof.

[0084] 6. The process according to any one of paragraphs 1 to 5, further comprising, heating the polymer gel at a temperature of about 25°C to about 150°C to produce a thermoset polymer.

[0085] 7. The process according to any one of paragraphs 1 to 5, further comprising heating the polymer gel at a temperature of about 600°C to about 1,800°C for about 30 seconds to about 10 hours to produce a porous carbonaceous material.

[0086] 8. The process according to any one of paragraphs 1 to 7, wherein the prepolymer has a solids content of about 40 wt% to about 99 wt% and a liquid content of about 1 wt% to 60 wt%.

[0087] 9. The process according to paragraph 8, wherein the liquid comprises water, an alcohol, ethylene glycol, polyethylene glycol, or a mixture thereof.

[0088] 10. The process according to any one of paragraphs 1 to 9, wherein the second catalyst comprises a carboxylic acid, an anhydride, a dihydroxybenzene, or a mixture thereof.

[0089] 1 1. The process according to paragraph 10 wherein the carboxylic acid comprises a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid, a pentacarboxylic acid, a hexacarboxylic acid, a polycarboxylic acid, or a mixture thereof. [0090] 12. The process according to any one of paragraphs 1 to 11, wherein the second catalyst comprises maleic anhydride, resorcinol, or a mixture thereof.

[0091] 13. The process according to any one of paragraphs 1 to 12, wherein the phenolic monomer comprises phenol, a first dihydroxybenzene, or a mixture thereof, and wherein the second catalyst comprises maleic anhydride, a second dihydroxybenzene, or a mixture thereof.

[0092] 14. The process according to any one of paragraphs 1 to 13, wherein the first catalyst comprises ammonia, dimethylethanolamine, ethylenediamine, triethylamine, trimethylamine, tripropylamine, diethylethanolamine, hexamethylenetetramine, lithium carbonate, or any mixture thereof.

[0093] 15. The process according to any one of paragraphs 1 to 14, wherein the aldehyde monomer comprises formaldehyde, furfural, or a mixture thereof.

[0094] 16. The process according to any one of paragraphs 1 to 15, wherein a molar ratio of the phenolic monomer to the aldehyde monomer in the first reaction mixture is about 0.1 : 1 to about 1.5: 1.

[0095] 17. The process according to any one of paragraphs 1 to 16, wherein reacting the first reaction mixture comprises heating the first reaction mixture to a temperature of about 40°C to about 200°C to produce the prepolymer.

[0096] 18. The process according to any one of paragraphs 1 to 17, wherein the first reaction mixture further comprises acetic acid, formic acid, nitric acid, citric acid, methane sulfonic acid, or a mixture thereof, and wherein the first reaction mixture has a pH of about 1 to about 5.

[0097] 19. The process according to any one of paragraphs 1 to 18, wherein the second reaction mixture comprises about 31 wt% to about 200 wt% of the second catalyst, based on a weight of the phenolic monomer.

[0098] 20. The process according to any one of paragraphs 1 to 19, wherein a molar ratio of the phenolic monomer to the second catalyst is about 0.001 : 1 to about 1 : 1.

[0099] 21. The process according to any one of paragraphs 1 to 20, wherein the prepolymer has a molecular weight of about 200 to about 2,000. [00100] 22. A process for making a polymer gel comprising: reacting a first reaction mixture comprising a phenolic monomer, an aldehyde monomer, and a first catalyst to produce a prepolymer; combining the prepolymer with a second catalyst and a carrier fluid to produce a second reaction mixture, wherein the second reaction mixture comprises greater than 30 wt% of the second catalyst based on a weight of the phenolic monomer; and polymerizing the prepolymer to produce polymer particles in gel form at a temperature of at least about 95°C in less than 25 minutes, as measured according to ASTM- D2471-99.

[00101] 23. The process according to paragraph 22, further comprising, contacting the polymer particles in gel form with a fluid comprising water, alcohol or a mixture thereof to produce a washed polymer particles in gel form.

[00102] 24. The process according to paragraph 22 or 23, further comprising, drying the washed polymer particles in gel form to produce dried polymer particles in gel form.

[00103] 25. The process according to paragraph 24, wherein the drying comprises heating, vacuum drying , freeze drying or a combination thereof.

[00104] 26. The process according to any one of paragraphs 22 to 25, further comprising, heating the polymer particles in gel form at a temperature of about 25°C to about 150°C to produce a thermoset polymer.

[00105] 27. The process according to any one of paragraphs 22 to 25, further comprising heating the polymer particles in gel form at a temperature of about 600°C to about 1,800°C for about 30 seconds to about 10 hours to produce a porous carbonaceous material.

[00106] 28. The process according to any one of paragraphs 22 to 27, wherein the prepolymer has a solids content of about 40 wt% to about 99 wt% and a liquid content of about 1 wt% to 60 wt%.

[00107] 29. The process according to paragraph 28, wherein the liquid comprises water, an alcohol, ethylene glycol, polyethylene glycol, or a mixture thereof.

[00108] 30. The process according to any one of paragraphs 22 to 30, wherein the second catalyst comprises a carboxylic acid, an anhydride, a dihydroxybenzene, or a mixture thereof. [00109] 31. The process according to paragraph 30, wherein the carboxylic acid comprises a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid, a pentacarboxylic acid, a hexacarboxylic acid, a polycarboxylic acid, or a mixture thereof.

[00110] 32. The process according to any one of paragraphs 22 to 31, wherein the second catalyst comprises maleic anhydride, resorcinol, or a mixture thereof.

[00111] 33. The process according to any one of paragraphs 22 to 32, wherein the phenolic monomer comprises phenol, a first dihydroxybenzene, or a mixture thereof, and wherein the second catalyst comprises maleic anhydride, a second dihydroxybenzene, or a mixture thereof.

[00112] 34. The process according to any one of paragraphs 22 to 33, wherein the first catalyst comprises ammonia, dimethylethanolamine, ethylenediamine, triethylamine, trimethylamine, tripropylamine, diethylethanolamine, hexamethylenetetramine, lithium carbonate, or any mixture thereof.

[00113] 35. The process according to any one of paragraphs 22 to 34, wherein the aldehyde monomer comprises formaldehyde, furfural, or a mixture thereof.

[00114] 36. The process according to any one of paragraphs 22 to 35, wherein a molar ratio of the phenolic monomer to the aldehyde monomer in the first reaction mixture is about 0.1 : 1 to about 1.5: 1.

[00115] 37. The process according to any one of paragraphs 22 to 36, wherein reacting the first reaction mixture comprises heating the first reaction mixture to a temperature of about 40°C to about 200°C to produce the prepolymer.

[00116] 38. The process according to any one of paragraphs 22 to 37, wherein the first reaction mixture further comprises acetic acid, formic acid, nitric acid, citric acid, methane sulfonic acid, or a mixture thereof, and wherein the first reaction mixture has a pH of about 1 to about 5.

[00117] 39. The process according to any one of paragraphs 22 to 38, wherein the second reaction mixture comprises about 31 wt% to about 200 wt% of the second catalyst, based on a weight of the phenolic monomer. [00118] 40. The process according to any one of paragraphs 22 to 39, wherein a molar ratio of the phenolic monomer to the second catalyst is about 0.001 : 1 to about 1 : 1.

[00119] 41. The process according to any one of paragraphs 22 to 40, wherein the prepolymer has a molecular weight of about 200 to about 2,000.

[00120] 42. The process according to any one of paragraphs 22 to 41, wherein the carrier fluid comprises mineral oil, vegetable oil, or a mixture thereof.

[00121] 43. The process according to any one of paragraph 22 or 42, wherein the carrier fluid has a viscosity of about 0.5 cP to about 1,000 cP at a temperature of 25°C.

[00122] 44. A process for making a polymer gel comprising: reacting a first reaction mixture comprising a phenolic monomer and formaldehyde in the presence of a first catalyst to produce a prepolymer, wherein the phenolic monomer comprises phenol, a first dihydroxybenzene, or a mixture thereof; combining a second catalyst with the prepolymer to produce a second reaction mixture, wherein the second reaction mixture comprises greater than 30 wt% of the second catalyst based on a weight of the phenolic monomer; and wherein the second catalyst comprises an anhydride, a second dihydroxybenzene, or a mixture thereof; polymerizing the prepolymer to produce the polymer gel at a temperature of at least about 95°C in less than 25 minutes, as measured according to ASTM- D2471-99; and heating the polymer gel at a temperature of about 600°C to about 1,800°C for about 30 seconds to about 10 hours to produce a porous carbonaceous material.

[00123] Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges including the combination of any two values, e.g., the combination of any lower value with any upper value, the combination of any two lower values, and/or the combination of any two upper values are contemplated unless otherwise indicated. Certain lower limits, upper limits and ranges appear in one or more claims below. All numerical values are "about" or "approximately" the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.

[00124] Various terms have been defined above. To the extent a term used in a claim is not defined above, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.

[00125] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

Claims: What is claimed is:

1. A process for making a polymer gel, comprising:

reacting a first reaction mixture comprising a phenolic monomer, an aldehyde monomer, and a first catalyst to produce a prepolymer;

combining a second catalyst with the prepolymer to produce a second reaction mixture, wherein the second reaction mixture comprises greater than 30 wt% of the second catalyst based on a weight of the phenolic monomer; and

polymerizing the prepolymer at a temperature of at least 95°C to produce the polymer gel in less than 25 minutes, as measured according to ASTM D2471 -99.

2. The process of claim 1, further comprising, heating the polymer gel at a temperature of about 25°C to about 150°C to produce a thermoset polymer.

3. The process of claim 1, further comprising, contacting the polymer gel with a fluid comprising water, alcohol or a mixture thereof to produce a washed polymer gel; and drying the washed polymer gel to produce a dried polymer gel, wherein the drying comprises heating, vacuum drying, freeze drying, or a combination thereof.

4. The process of claim 1, further comprising heating the polymer gel at a temperature of about 600°C to about 1,800°C for about 30 seconds to about 10 hours to produce a porous carbonaceous material.

5. The process of claim 1, wherein the prepolymer has a solids content of about 40 wt% to about 99 wt% and a liquid content of about 1 wt% to 60 wt%.

6. The process of claim 5, wherein the liquid comprises water, an alcohol, ethylene glycol, polyethylene glycol, or a mixture thereof.

7. The process of claim 1, wherein the second catalyst comprises a carboxylic acid, an anhydride, a dihydroxybenzene, or a mixture thereof.

8. The process of claim 7, wherein the carboxylic acid comprises a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid, a pentacarboxylic acid, a hexacarboxylic acid, a polycarboxylic acid, or a mixture thereof.

9. The process of claim 1, wherein the second catalyst comprises maleic anhydride, resorcinol, or a mixture thereof.

10. The process of claim 1, wherein the phenolic monomer comprises phenol, a first dihydroxybenzene, or a mixture thereof; wherein the second catalyst comprises maleic anhydride, a second dihydroxybenzene, or a mixture thereof; and wherein the aldehyde monomer comprises formaldehyde, furfural, or a mixture thereof.

11. The process of claim 1, wherein a molar ratio of the phenolic monomer to the aldehyde monomer in the first reaction mixture is about 0.1 : 1 to about 1.5: 1.

12. The process of claim 1, wherein the second reaction mixture comprises about 31 wt% to about 200 wt% of the second catalyst, based on a weight of the phenolic monomer.

13. The process of claim 1, wherein a molar ratio of the phenolic monomer to the second catalyst is about 0.001 : 1 to about 1 : 1.

14. The process of claim 1, wherein the prepolymer has a molecular weight of about 200 to about 2,000.

15. A process for making a polymer gel comprising:

reacting a first reaction mixture comprising a phenolic monomer and formaldehyde in the presence of a first catalyst to produce a prepolymer, wherein the phenolic monomer comprises phenol, a first dihydroxybenzene or a mixture thereof;

combining a second catalyst with the prepolymer to produce a second reaction mixture, wherein the second reaction mixture comprises greater than 30 wt% of the second catalyst based on a weight of the phenolic monomer; and wherein the second catalyst comprises an anhydride, a second dihydroxybenzene, or a mixture thereof; and polymerizing the prepolymer at a temperature of at least 95°C to produce the polymer gel in less than 25 minutes, as measured according to ASTM D2471-99.

16. A process for making a polymer gel comprising:

combining the prepolymer with a second catalyst and a carrier fluid to produce a second reaction mixture, wherein the second reaction mixture comprises greater than 30 wt% of the second catalyst based on a weight of the phenolic monomer; and

polymerizing the prepolymer to produce polymer particles in gel form in less than 25 minutes, at a temperature of at least 95°C, as measured according to ASTM D2471-99.

17. The process of claim 16, wherein the carrier fluid comprises mineral oil, vegetable oil, or a mixture thereof; and wherein the carrier fluid has a viscosity of about 0.5 cP to about 1,000 cP at a temperature of 25°C.

18. The process of claim 16, wherein the second catalyst comprises a carboxylic acid, an anhydride, a dihydroxybenzene, or a mixture thereof.

19. The process of claim 16, further comprising heating the polymer particles in gel form at a temperature of about 600°C to about 1,800°C for about 30 seconds to about 10 hours to produce a porous carbonaceous material.

20. The process of claim 16, wherein the second reaction mixture comprises about 31 wt% to about 200 wt% of the second catalyst, based on a weight of the phenolic monomer.