Preparation of polymeric resins and carbon materials
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 can have enhanced electrochemical properties and find utility in any number of electrical devices, for example, as electrode material in ultracapacitors or batteries.
1. A method for making polymer particles in gel form via an emulsion or suspension process, comprising:
contacting a carrier fluid and a monomer component containing one or more phenolic monomers to make an emulsion or a suspension; and
polymerizing the monomer component in the emulsion or the suspension to make the polymer particles in gel form, wherein:
the carrier fluid contains less than 50 wt % cyclohexane, based on the total weight of the carrier fluid,
the carrier fluid has a viscosity of 1 cP to about 500 cP at a temperature of about 25° C.,
the monomer component has a viscosity of about 5 cP to about 1,000 cP at a temperature of about 25° C.,
a Dv,50 of the polymer particles in gel form is greater than or equal to 1 mm, and
the polymer particles in gel form having the Dv,50 of greater than or equal to 1 mm are made without milling, grinding, or other physical means of particle sizing.
2. The method of claim 1 , wherein the Dv,50 of the polymer particles in gel form is about 3 mm to about 7 mm.
3. A method for making polymer particles in gel form via an emulsion or suspension process, comprising:
contacting a carrier fluid and a monomer component containing one or more phenolic monomers to make an emulsion or a suspension, 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; and
polymerizing the monomer component in the emulsion or the suspension to make the polymer particles in gel form, wherein:
the carrier fluid contains less than 50 wt % cyclohexane, based on the total weight of the carrier fluid,
the carrier fluid has a viscosity of about 1 cP to about 500 cP at a temperature of about 25° C.,
the monomer component has a viscosity of about 5 cP to about 1,000 cP at a temperature of about 25° C., and
a Dv,50 of the polymer particles in gel form is greater than or equal to 1 mm.
4. The method of claim 1 , wherein:
the monomer component is an aqueous mixture and further one or more catalysts,
the Dv,50 of the polymer particles in gel form is greater than 1 mm to about 7 mm,
the polymer particles in gel form have a span of less than 3,
the span is equal to (a Dv,90−a Dv,10)/a Dv,50, and
the Dv,10, the Dv,50, and the Dv,90 are the volume particle sizes measured at 10%, 50% and 90%, respectively, of the particle size distribution.
5. The method of claim 1 , wherein the monomer component is an aqueous mixture and further comprises ammonium acetate, acetic acid, or a mixture thereof.
6. The method of claim 1 , further comprising agitating the emulsion or the suspension during polymerization of the monomer component, wherein:
the one or more phenolic monomers comprises monohydroxybenzene, 1,3-dihydroxybenzene, or a 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, and
the Dv,50 of the polymer particles in gel form is greater than 1 mm to about 7 mm.
7. The method of claim 1 , further comprising heating the emulsion or the suspension to a temperature of about 30° C. to about 150° C., wherein:
the one or more phenolic monomers comprises monohydroxybenzene, 1,3-dihydroxybenzene, or a mixture thereof,
the monomer component is an aqueous mixture and further comprises ammonium acetate, acetic acid, or a 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, and
the Dv,50 of the polymer particles in gel form is greater than 1 mm to about 7 mm.
8. The method of claim 1 , wherein the monomer component has a pH of less than 7 during polymerization.
9. The method of claim 1 , wherein:
the monomer component further contains one or more crosslinking monomers.
10. The method of claim 1 , wherein the emulsion or the suspension further comprises 0.01% to 20% of a non-ionic surfactant having a molecular weight of from about 100 Daltons to about 2,000 Daltons.
11. 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.
12. The method of claim 11 , wherein the pyrolyzed particles have a total pore volume greater than 0.5 cm 3 /g and a gerameter (GM) greater than or equal to 21.
13. A method for making polymer particles in gel form via an emulsion or suspension process, comprising:
contacting a carrier fluid and a monomer component containing one or more phenolic monomers to make an emulsion or a suspension; and
polymerizing the monomer component in the emulsion or the suspension to make the polymer particles in gel form, wherein:
the carrier fluid is free of surfactant or contains a surfactant at a concentration less than the critical micelle concentration,
the carrier fluid has a viscosity of about 1 cP to about 500 cP at a temperature of about 25° C.,
the monomer component has a viscosity of about 5 cP to about 1,000 cP at a temperature of about 25° C.,
a Dv,50 of the polymer particles in gel form is greater than or equal to 1 mm, and
the polymer particles in gel form having the Dv,50 of greater than or equal to 1 mm are made without milling, grinding, or other physical means of particle sizing.
14. The method of claim 13 , wherein:
the viscosity of the carrier fluid is about 10 cP to about 100 cP at a temperature of about 25° C., the viscosity of the monomer component is about 5 cP to about 600 cP at a temperature of about 25° C., and
the Dv,50 of the polymer particles in gel form is greater than or equal to 1 mm to about 7 mm.
15. The method of claim 13 , wherein the carrier fluid has a boiling point of 81° C. or greater at a pressure of 100 kPa.
16. The method of claim 13 , wherein the monomer component is an aqueous mixture and further comprises ammonium acetate, acetic acid, or a mixture thereof.
17. The method of claim 16 , wherein the monomer component comprises the mixture of ammonium acetate and acetic acid.
18. The method of claim 13 , further comprising separating the polymer particles in gel form having the Dv,50 of greater than or equal to 1 mm from the carrier fluid by filtration, decanting, or a combination of filtration and decanting.
19. The method of claim 13 , wherein the monomer component has a pH of greater than 7 during polymerization.
20. The method of claim 13 , wherein the emulsion or the suspension is at a temperature of about 30° C. or more when the monomer component polymerizes to make the polymer particles in gel form, and wherein the Dv,50 of the polymer particles in gel form is greater than 1 mm.
21. The method of claim 13 , wherein:
the monomer component further contains one or more crosslinking monomers,
and
the Dv,50 of the polymer particles in gel form is greater than or equal to 1 mm to about 7 mm.
22. The method of claim 13 , wherein the monomer component further comprises a nitrogen-containing electrochemical modifier.
23. The method of claim 13 , further comprising drying the polymer particles in gel form without any size reduction of the polymer particles in gel form.
24. The method of claim 13 , wherein the polymer particles in gel form have a total pore volume of between about 0.01 cm 3 /g and 1.5 cm 3 /g.
25. The method of claim 13 , further comprising:
heating the polymer particles in gel form in an inert atmosphere at temperatures ranging from 500° C. to 2400° 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 1300° C. to produce activated particles.
26. The method of claim 25 , wherein the activated particles have a total pore volume greater than 0.5 cm 3 /g and gerameter (GM) is greater than or equal to 21.
27. The method of claim 25 , wherein the activated particles have a total pore volume greater than 1 cm 3 /g and gerameter (GM) is from 9 to 21.
28. The method of claim 1 , wherein:
the viscosity of the carrier fluid is about 10 cP to about 100 cP at a temperature of about 25° C.,
the viscosity of the monomer component is about 5 cP to about 100 cP at a temperature of about 25° C., and
the Dv,50 of the polymer particles in gel form is 1.5 mm to about 7 mm.
29. The method of claim 1 , further comprising separating the polymer particles in gel form having the Dv,50 of greater than or equal to 1 mm from the carrier fluid by filtration, decanting, or a combination of filtration and decanting.
30. The method of claim 9 , wherein the one or more crosslinking monomers comprises formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfuraldehyde, benzaldehyde, glutaraldehyde, or any mixture thereof.
31. A method for making polymer particles in gel form via an emulsion or suspension process, comprising:
contacting a carrier fluid and a monomer component comprising resorcinol and formaldehyde to make an emulsion or a suspension;
polymerizing the monomer component in the emulsion or the suspension to make the polymer particles in gel form, wherein the polymer particles in gel form have a Dv,50 of 1 mm to about 7 mm; and
separating the polymer particles in gel form having the Dv,50 of 1 mm to about 7 mm from the carrier fluid by filtration, decanting, or a combination of filtration and decanting, wherein:
the carrier fluid contains less than 50 wt % cyclohexane, based on the total weight of the carrier fluid,
the carrier fluid is free of surfactant or contains a surfactant at a concentration less than the critical micelle concentration,
the carrier fluid has a viscosity of about 1 cP to about 500 cP at a temperature of about 25° C.,
the monomer component has a viscosity of about 5 cP to about 1,000 cP at a temperature of about 25° C.,
the polymer particles in gel form having the Dv,50 of 1 mm to about 7 mm are made without milling, grinding, or other physical means of particle sizing,
the polymer particles in gel form have a span of less than 3,
the span is equal to (a Dv,90−a Dv,10)/a Dv,50, and
the Dv,10, the Dv,50, and the Dv,90 are the volume particle sizes measured at 10%, 50% and 90%, respectively, of the particle size distribution.
32. The method of claim 31 , wherein the monomer component is an aqueous mixture and further comprises ammonium acetate, acetic acid, or a mixture thereof.
33. The method of claim 1 , wherein the monomer component further contains one or more crosslinking compounds, and wherein:
the one or more phenolic monomers comprises monohydroxybenzene, 1,3-dihydroxybenzene, or a mixture thereof,
the one or more crosslinking monomers comprises formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfuraldehyde, benzaldehyde, glutaraldehyde, or any mixture thereof, and
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.
34. The method of claim 1 , wherein the carrier fluid has a viscosity of about 25 cP to about 500 cP at a temperature of about 25° C.
35. The method of claim 21 , wherein the one or more crosslinking monomers comprises formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfuraldehyde, benzaldehyde, glutaraldehyde, or any mixture thereof.