Methods for making wet gels and dried gels therefrom
View Patent ↗Methods for making wet gels and dried gels therefrom are provided. The method for making a wet gel can include combining a hydroxybenzene compound, an aldehyde compound, and an additive to produce a reaction mixture. The additive can include a carboxylic acid, an anhydride, a homopolymer, a copolymer, or any mixture thereof. At least the hydroxybenzene compound and the aldehyde compound can be reacted to produce a wet gel. The reaction mixture can include about 10 wt % to about 65 wt % of the hydroxybenzene compound, about 5 wt % to about 25 wt % of the aldehyde compound, up to about 85 wt % of the carboxylic acid, up to about 40 wt % of the anhydride, up to about 40 wt % of the homopolymer, and up to about 40 wt % of the copolymer, where weight percent values are based on the combined weight of the hydroxybenzene compound, the aldehyde compound, and the additive.
1. A method for making a wet gel, comprising:
combining a hydroxybenzene compound, an aldehyde compound, and an additive to produce a reaction mixture, wherein the additive comprises a carboxylic acid and an anhydride; and
reacting at least the hydroxybenzene compound and the aldehyde compound to produce a wet gel, wherein the reaction mixture comprises about 10 wt % to about 65 wt % of the hydroxybenzene compound, about 5 wt % to about 25 wt % of the aldehyde compound, about 0.1 wt % to about 85 wt % of the carboxylic acid, and about 0.1 wt % to about 40 wt % of the anhydride, wherein the reaction mixture comprises about 10 wt % to about 90 wt % of the additive, and wherein all weight percent values are based on the combined weight of the hydroxybenzene compound, the aldehyde compound, and the additive; and
drying the wet gel to produce a dried gel, wherein the dried gel has at least one property selected from the group consisting of:
an average pore size of about 10 nm to about 150 nm,
a specific surface area of about 5 m 2 /g to about 1,500 m 2 /g, and
a pore volume of about 0.2 cm 3 /g to about 2.5 cm 3 /g.
2. The method of claim 1 , further comprising combining at least one solvent with the hydroxybenzene compound, the aldehyde compound, and the additive to produce the reaction mixture, wherein a pressure exerted on the wet gel during drying is maintained below a critical pressure of the solvent.
3. The method of claim 1 , wherein the hydroxybenzene compound comprises phenol, resorcinol, cresol, catechol, hydroquinone, phloroglucinol, or any mixture thereof, and wherein the aldehyde compound comprises formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfuraldehyde, glucose, benzaldehyde, cinnamaldehyde, or any mixture thereof.
4. The method of claim 1 , wherein the hydroxybenzene compound comprises phenol, resorcinol, cresol, catechol, hydroquinone, phloroglucinol, or any mixture thereof, wherein the aldehyde compound comprises formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfuraldehyde, glucose, benzaldehyde, cinnamaldehyde, or any mixture thereof, and wherein the additive comprises acetic acid, citric acid, and maleic anhydride.
5. The method of claim 1 , further comprising:
combining at least one solvent with the hydroxybenzene compound, the aldehyde compound, and the additive to produce the reaction mixture, wherein:
a pressure exerted on the wet gel during drying is maintained below a critical pressure of the solvent,
the hydroxybenzene compound comprises phenol, resorcinol, cresol, catechol, hydroquinone, phloroglucinol, or any mixture thereof,
the aldehyde compound comprises formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfuraldehyde, glucose, benzaldehyde, cinnamaldehyde, or any mixture thereof,
the additive comprises acetic acid, citric acid, and maleic anhydride, and
the solvent comprises water.
6. A method for making a dried gel, comprising:
combining a solvent, a hydroxybenzene compound, an aldehyde compound, and an additive to produce a reaction mixture, wherein the additive comprises a carboxylic acid and an anhydride;
reacting at least the hydroxybenzene compound and the aldehyde compound to produce a wet gel; and
drying the wet gel to produce a dried gel, wherein a pressure exerted on the wet gel during drying is maintained below a critical pressure of the solvent, and wherein the dried gel has at least one property selected from the group consisting of:
an average pore size of about 10 nm to about 150 nm,
a specific surface area of about 5 m 2 /g to about 1,500 m 2 /g, and
a pore volume of about 0.2 cm 3 /g to about 2.5 cm 3 /g.
7. A method for making a dried gel, comprising:
determining one or more desired properties of a dried gel selected from the group consisting of: an average pore size of about 10 nm to about 150 nm, a specific surface area of about 5 m 2 /g to about 1,500 m 2 /g, and a pore volume of about 0.2 cm 3 /g to about 2.5 cm 3 /g;
combining a solvent, a hydroxybenzene compound, an aldehyde compound, and an additive to produce a reaction mixture, wherein the additive comprises a carboxylic acid and an anhydride;
reacting at least the hydroxybenzene compound and the aldehyde compound to produce a wet gel; and
drying the wet gel to produce a dried gel, wherein a pressure exerted on the wet gel during drying is maintained below a critical pressure of the solvent, and wherein the amount of the hydroxybenzene compound, the amount of the aldehyde compound, and the amount of the additive are controlled to produce the dried gel having the one or more desired properties.
8. The method of claim 1 , wherein the reaction mixture comprises about 25 wt % to about 70 wt % of the carboxylic acid and about 0.5 wt % to about 10 wt % of the anhydride, based on the combined weight of the hydroxybenzene compound, the aldehyde compound, and the additive.
9. The method of claim 1 , wherein the anhydride comprises maleic anhydride, 1,2,4-benzenetricarboxylic anhydride, phthalic anhydride, succinic anhydride, or any mixture thereof.
10. The method of claim 1 , wherein the carboxylic acid comprises a polycarboxylic acid.
11. The method of claim 10 , wherein the polycarboxylic acid comprises citric acid.
12. The method of claim 1 , wherein the reaction mixture further comprises a polyol.
13. The method of claim 12 , wherein the polyol comprises diethanolamine, triethanolamine, ethyl diethanolamine, methyl diethanolamine, or any mixture thereof.
14. The method of claim 1 , wherein the reaction mixture further comprises about 1 wt % to about 5 wt % of water, based on a combined weight of the hydroxybenzene compound, the aldehyde compound, the additive, and the water.
15. The method of claim 1 , wherein the reaction mixture further comprises about 0.01 wt % to about 90 wt % of a modifier, based on a combined weight of the hydroxybenzene compound, the aldehyde compound, the additive, and the modifier, and wherein the modifier comprises lead, tin, antimony, bismuth, arsenic, tungsten, silver, zinc, cadmium, indium, silicon, iron, sulfur, cobalt, nickel, bromine, chlorine, ruthenium, rhodium, platinum, palladium, zirconium, gold, or any mixture thereof.
16. The method of claim 1 , wherein at least a portion of the hydroxybenzene compound and at least a portion of the aldehyde compound are reacted with one another to form a prepolymer, and wherein the prepolymer is reacted in the presence of the additive to produce the wet gel.
17. The method of claim 1 , wherein at least a portion of the hydroxybenzene compound and at least a portion of the aldehyde compound are reacted with one another to form a prepolymer, and wherein the prepolymer is reacted with the additive to produce the wet gel.
18. The method of claim 1 , wherein the additive further comprises about 0.5 wt % to about 10 wt % of a homopolymer, based on a combined weight of the hydroxybenzene compound, the aldehyde compound, and the additive, and wherein the homopolymer comprises polyethylene, polypropylene, polystyrene, polyvinylchloride, or a mixture thereof.
19. The method of claim 1 , wherein the additive further comprises about 0.1 wt % to about 10 wt % of a copolymer, based on the combined weight of the hydroxybenzene compound, the aldehyde compound, and the additive, and wherein the copolymer comprises poly[styrene-alt-(maleic anhydride)], poly[(ethylene glycol)-alt-(terephthalic acid; isophthalic acid)], poly(1,3,6-trioxacyclooctane) poly(oxymethyleneoxyethyleneoxyethylene), poly(styrene-stat-acrylonitrile-stat-butadiene), poly[(6-aminohexanoic acid)-stat-(7-aminoheptanoic acid)], poly[(4-hydroxybenzoic acid)-co-hydroquinone-co-(terephthalic acid)], poly[styrene-co-(methyl methacrylate)], acrylonitrile-butadiene-styrene terpolymer, polystyrene-block-polybutadiene-block-polystyrene, poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) block polymer, poly[poly(methyl methacrylate)-block-polystyrene-block-poly(methyl acrylate)], a copolymer of ethylene and one or more C 3 to C 20 alpha olefin comonomers, a branched methacrylate copolymer, or any mixture thereof.
20. The method of claim 1 , wherein:
the reaction mixture further comprises a solvent,
the hydroxybenzene compound comprises phenol, resorcinol, or a mixture thereof,
the aldehyde compound comprises formaldehyde,
the carboxylic acid comprises acetic acid,
the anhydride comprises maleic anhydride,
the solvent comprises water,
the reaction mixture comprises about 25 wt % to about 70 wt % of the carboxylic acid and about 0.5 wt % to about 10 wt % of the anhydride, based on the combined weight of the hydroxybenzene compound, the aldehyde compound, and the additive,
the reaction mixture comprises about 1 wt % to about 5 wt % of the solvent, based on a combined weight of the hydroxybenzene compound, the aldehyde compound, the additive, and the solvent, and
a pressure exerted on the wet gel during drying is maintained below a critical pressure of the solvent.