Emulsion and suspension polymerization processes, and improved electrochemical performance for carbon derived from same
View Patent ↗The present application is directed to methods for preparation of polymer particles in gel form and carbon materials made therefrom. The carbon materials comprise enhanced electrochemical properties and find utility in any number of electrical devices, for example, as electrode material in ultracapacitors or batteries. The methods herein can also be employed generally to improve emulsion and/or suspension polymerization processes by improved control of diffusion of acidic and basic species between the polymer and secondary phases.
1. A method for making polymer particles in gel form via an emulsion or suspension process, the method comprising preparing a reactant mixture comprising a monomer component containing one or more phenolic compounds and one or more crosslinking compounds, and a carrier fluid, wherein:
the carrier fluid contains less than 50 wt % cyclohexane, based on the total weight of the carrier fluid,
the monomer component polymerizes to form the polymer particles in gel form,
the carrier fluid comprises an acid, a base, a catalyst, or a combination thereof, at a concentration for each species of at least 50% of the saturation limit, and
a volume average particle size (Dv,50) of the polymer particles in gel form is greater than or equal to 1 mm.
2. The method of claim 1 , wherein the volume average particle size (Dv,50) of the polymer particles in gel form is greater than or equal to 1 mm to about 6 mm.
3. The method of claim 1 , wherein the one or more phenolic compounds comprise phenol, resorcinol, catechol, hydroquinone, phloroglucinol, or any mixture thereof, and wherein the one or more crosslinking compounds comprise formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfuraldehyde, benzaldehyde, glutaraldehyde, glyoxal, glyoxylic acid, a glyoxylic acid ester, a glyoxylic acid amide, 5-(hydroxymethyl)furfural, or any mixture thereof.
4. The method of claim 1 , wherein:
the one or more phenolic compounds comprise phenol, resorcinol, catechol, hydroquinone, phloroglucinol, or any mixture thereof,
the one or more crosslinking compounds comprise formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfuraldehyde, benzaldehyde, glutaraldehyde, glyoxal, glyoxylic acid, a glyoxylic acid ester, a glyoxylic acid amide, 5-(hydroxymethyl)furfural, or any mixture thereof,
the carrier fluid comprises one or more vegetable oils, one or more mineral oils, one or more chlorinated hydrocarbons, one or more paraffinic oils, or any mixture thereof,
the carrier fluid comprises the catalyst,
the catalyst comprises acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid, a sulfonic acid, gallic acid, oxalic acid, picric acid, ammonium carbonate, ammonium bicarbonate, ammonium acetate, ammonium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, hexamethylenetetramine, or any mixture thereof, and
the volume average particle size (Dv,50) of the polymer particles in gel form is greater than or equal to 1 mm to about 6 mm.
5. The method of claim 4 , wherein the one or more phenolic compounds and the one or more crosslinking compounds are prepolymerized with one another to form a prepolymer prior to making the polymer particles in gel form via the emulsion or suspension process.
6. The method of claim 1 , wherein the carrier fluid comprises one or more vegetable oils, one or more mineral oils, one or more chlorinated hydrocarbons, one or more paraffinic oils, or any mixture thereof.
7. The method of claim 1 , wherein the carrier fluid comprises the catalyst, and wherein the catalyst comprises acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid, a sulfonic acid, gallic acid, oxalic acid, picric acid, ammonium carbonate, ammonium bicarbonate, ammonium acetate, ammonium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, hexamethylenetetramine, or any mixture thereof.
8. The method of claim 1 , further comprising:
heating the polymer particles in gel form in an inert atmosphere at a temperature of from 500° C. to 2,400° C. to produce pyrolyzed particles; and
activating the pyrolzyed particles in an atmosphere comprising carbon dioxide, carbon monoxide, steam, oxygen, or any mixture thereof at a temperature of from 500° C. to 1,300° C. to produce activated particles.
9. The method of claim 8 , wherein the activated particles have a total pore volume of greater than 0.5 cm 3 /g and a gerameter (GM) of greater than or equal to 24.
10. The method of claim 1 , wherein the reactant mixture further comprises a nitrogen-containing electrochemical modifier.
11. The method of claim 1 , wherein the one or more phenolic compounds and the one or more crosslinking compounds are prepolymerized with one another to form a prepolymer prior to making the polymer particles in gel form via the emulsion or suspension process.
12. The method of claim 1 , wherein the reaction mixture further comprises 0.01 wt % to 20 wt % of a non-ionic surfactant having a molecular weight of from about 100 Daltons to about 2,000 Daltons.
13. The method of claim 1 , further comprising heating the polymer particles in gel form in an inert atmosphere at a temperature of from about 500° C. to about 2,400° C. to produce pyrolyzed particles.
14. A method for making polymer particles in gel form via an emulsion or suspension process, the method comprising preparing a reactant mixture comprising a monomer component containing one or more phenolic compounds and one or more crosslinking compounds, and a carrier fluid, wherein:
the monomer component polymerizes to form the polymer particles in gel form,
the carrier fluid is free of or contains a surfactant at a concentration less than the critical micelle concentration,
the carrier fluid comprises an acid, a base, a catalyst, or a combination thereof, at a concentration for each species of at least 50% of the saturation limit, and
a volume average particle size (Dv,50) of the polymer particles in gel form is greater than or equal to 1 mm.
15. The method of claim 14 , wherein the carrier fluid comprises one or more vegetable oils, one or more mineral oils, one or more chlorinated hydrocarbons, one or more paraffinic oils, or any mixture thereof.
16. The method of claim 14 , wherein the one or more phenolic compounds and the one or more crosslinking compounds are prepolymerized with one another to form a prepolymer prior to making the polymer particles in gel form via the emulsion or suspension process.
17. The method of claim 14 , wherein the volume average particle size (Dv,50) of the polymer particles in gel form is greater than or equal to 1 mm to about 6 mm.
18. The method of claim 14 , wherein the one or more phenolic compounds comprise phenol, resorcinol, catechol, hydroquinone, phloroglucinol, or any mixture thereof, and wherein the one or more crosslinking compounds comprise formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfuraldehyde, benzaldehyde, glutaraldehyde, glyoxal, glyoxylic acid, a glyoxylic acid ester, a glyoxylic acid amide, 5-(hydroxymethyl)furfural, or any mixture thereof.
19. The method of claim 14 , wherein the carrier fluid comprises the catalyst, and wherein the catalyst comprises acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid, a sulfonic acid, gallic acid, oxalic acid, picric acid, ammonium carbonate, ammonium bicarbonate, ammonium acetate, ammonium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, hexamethylenetetramine, or any mixture thereof.
20. The method of claim 14 , wherein:
the one or more phenolic compounds comprise phenol, resorcinol, catechol, hydroquinone, phloroglucinol, or any mixture thereof,
the one or more crosslinking compounds comprise formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfuraldehyde, benzaldehyde, glutaraldehyde, glyoxal, glyoxylic acid, a glyoxylic acid ester, a glyoxylic acid amide, 5-(hydroxymethyl)furfural, or any mixture thereof,
the carrier fluid comprises one or more vegetable oils, one or more mineral oils, one or more chlorinated hydrocarbons, one or more paraffinic oils, or any mixture thereof,
the carrier fluid comprises the catalyst,
the catalyst comprises acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid, a sulfonic acid, gallic acid, oxalic acid, picric acid, ammonium carbonate, ammonium bicarbonate, ammonium acetate, ammonium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, hexamethylenetetramine, or any mixture thereof, and
the volume average particle size (Dv,50) of the polymer particles in gel form is greater than or equal to 1 mm to about 6 mm.