Methods for making wet gels and dried gels therefrom

Patent metadata

Field	Value
Publication number	US-9926401-B2
Application number	US-201715462414-A
Country	US
Kind code	B2
Filing date	Mar 17, 2017
Priority date	Sep 20, 2013
Publication date	Mar 27, 2018
Grant date	Mar 27, 2018

Abstract

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.

First claim

What is claimed is:

1. A process for making a wet gel, comprising:
mixing a hydroxybenzene compound, an aldehyde compound and an additive that comprises an anhydride to provide a reaction mixture;
reacting at least the hydroxybenzene compound and the aldehyde compound in the reaction mixture 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, and up to about 40 wt % of the anhydride, based on the combined weight of the hydroxybenzene compound, the aldehyde compound, and the additive.

2. The process of claim 1 , wherein the additive further comprises a carboxylic acid.

3. The process of claim 2 , wherein the reaction mixture comprises about 25 wt % to about 75 wt % of the carboxylic acid, based on the combined weight of the hydroxybenzene compound, the aldehyde compound, and the additive.

4. The process of claim 3 , wherein the reaction mixture comprises about 35 wt % to about 85 wt % of the additive, based on the combined weight of the hydroxybenzene compound, the aldehyde compound, and the additive.

5. The process of claim 1 , wherein the reaction mixture comprises 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.

6. The process of claim 1 , wherein the additive further comprises a homopolymer, wherein the reaction mixture comprises about 0.5 wt % to about 10 wt % of the homopolymer, based on the 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.

7. The process of claim 1 , wherein the additive further comprises a copolymer, wherein the reaction mixture comprises about 1 wt % to about 10 wt % of the 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 a mixture thereof.

8. The process of claim 1 , wherein the additive further comprises a carboxylic acid and a copolymer, and wherein the reaction mixture comprises about 0.1 wt % to about 10 wt % of the anhydride, about 30 wt % to about 70 wt % of the carboxylic acid, and about 0.1 wt % to about 8 wt % of the copolymer, based on the combined weight of the hydroxybenzene compound, the aldehyde compound, and the additive.

9. The process 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.

10. The process of claim 1 , further comprising combining at least one polyol with the hydroxybenzene compound, the aldehyde compound, and the additive to produce the reaction mixture, wherein the reaction mixture comprises about 0.1 wt % to about 40 wt % of the polyol, based on the combined weight of the hydroxybenzene compound, the aldehyde compound, the additive, and the polyol, and wherein the polyol comprises diethanolamine, triethanolamine, ethyl diethanolamine, methyl diethanolamine, or a mixture thereof.

11. The process of claim 1 , further comprising combining at least one modifier with the hydroxybenzene compound, the aldehyde compound, and the additive to produce the reaction mixture, wherein the reaction mixture comprises about 0.1 wt % to about 95 wt % of the modifier, based on the 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, oxides thereof, or a mixture thereof.

12. The process of claim 1 , wherein the hydroxybenzene compound comprises phenol, resorcinol, cresol, catechol, hydroquinone, phloroglucinol, or a mixture thereof, wherein the aldehyde compound comprises formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfuraldehyde, glucose, benzaldehyde, cinnamaldehyde, or a mixture thereof, and wherein the anhydride comprises maleic anhydride, phthalic anhydride, acetic anhydride, succinic anhydride, naphthalic anhydride, 1,2,4-benzenetricarboxylic anhydride, or a mixture thereof.

13. The process of claim 1 , wherein the wet gel comprises a network of polymer chains having one or more pores that are at least partially filled by a liquid.

14. The process of claim 1 , wherein the wet gel comprises a network of polymer chains having one or more pores that are filled by a liquid.

15. The process of claim 1 , wherein the wet gel is a hydrogel comprising a network of polymer chains having one or more pores that are at least partially filled by water.

16. A process for making a wet gel, comprising:
mixing a hydroxybenzene compound, an aldehyde compound, a solvent, and an additive to provide a reaction mixture;
reacting at least the hydroxybenzene compound and the aldehyde compound in the reaction mixture to produce a wet gel, wherein:
the additive comprises a carboxylic acid and an anhydride,
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 25 wt % to about 75 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 35 wt % to about 85 wt % of the additive, based on the combined weight of the hydroxybenzene compound, the aldehyde compound, and the additive, and
the reaction mixture comprises about 1 wt % to about 60 wt % of the solvent, based on the combined weight of the hydroxybenzene compound, the aldehyde compound, the solvent, and the additive.

17. The process of claim 16 , wherein:
the hydroxybenzene compound comprises phenol, resorcinol, or a mixture thereof,
the aldehyde compound comprises formaldehyde,
the solvent comprises water,
the carboxylic acid comprises acetic acid, citric acid, or a mixture thereof,
the anhydride comprises maleic anhydride, succinic anhydride, or a mixture thereof,
the wet gel comprises a network of polymer chains having one or more pores that are at least partially filled by the solvent.

18. The process of claim 16 , 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 or with the additive to produce the wet gel.

Assignees

• Georgia Pacific Chemicals Llc

Inventors

• Dong Xing
• Qureshi Shahid P
• Lee Christopher M
• Shoemake Kelly A
• Ludvik Joseph Frank

Classifications

• C01B32/318

  characterised by the starting materials · CPC title

• C08G81/00

  Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers (involving only carbon-to-carbon unsaturated bond reactions C08F299/00 {; polyester-amides C08G69/44; polyester-imides C08G73/16; polyamides-imides C08G73/14; block- or graft polymers containing polysiloxane sequences C08G77/42}) · CPC title

• C08G8/28 Primary

  Chemically modified polycondensates · CPC title

• C08G8/32

  by organic acids or derivatives thereof, e.g. fatty oils · CPC title

• C08J2201/0504

  the liquid phase being aqueous · CPC title