Preparation of phenol-formaldehyde resin beads using suspension or emulsion polymerization

• US 9,133,295 B2
• Filed: 11/27/2013
• Issued: 09/15/2015
• Est. Priority Date: 11/29/2012
• Status: Expired due to Fees

• Current Assignee: Georgia-Pacific Chemicals LLC (KOCH Industries Incorporated)
• Original Assignee: Georgia-Pacific Chemicals LLC (KOCH Industries Incorporated)
• Inventors: Qureshi, Shahid P., Dong, Xing, Chan, Charles C., Ludvik, Joseph Frank
• Primary Examiner(s): Boyle, Robert C
• Application Number:
  US14/092,267
• Publication Number:
  US 20140148560A1
• Time in Patent Office: 657 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C08G 8/10 with phenol
• CPC Class Codes: C08G 8/22 Resorcinol
• CPC Class Codes: C08G 8/32 by organic acids or derivatives thereof, e.g. fatty oils
• CPC Class Codes: C08G 85/004 Modification of polymers by chemical after-treatment
• CPC Class Codes: C08J 2201/026 Crosslinking before of after foaming
• CPC Class Codes: C08J 2201/0482 the liquid phase being organic
• CPC Class Codes: C08J 2201/0502 the liquid phase being organic
• CPC Class Codes: C08J 2205/02 the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
• CPC Class Codes: C08J 2361/06 of aldehydes with phenols
• CPC Class Codes: C08J 9/16 Making expandable particles
• CPC Class Codes: C08J 9/28 by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum

Abstract

Methods for making polymer particles in gel form via an emulsion and/or suspension polymerization are provided. In at least one specific embodiment, the method can include reacting a first reaction mixture comprising a phenolic monomer, an aldehyde monomer, and a first catalyst to produce a prepolymer. The method can also include combining the prepolymer with a carrier fluid and a second catalyst to produce a second reaction mixture. The second catalyst can include a dicarboxylic acid, an anhydride, a dihydroxybenzene, or any mixture thereof. The method can also include polymerizing the prepolymer to form polymer particles in gel form.

Claims

1. A method for making polymer particles in gel form via emulsion or suspension polymerization, the method 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 carrier fluid and a second catalyst to produce a second reaction mixture, wherein the second catalyst comprises a dicarboxylic acid, an anhydride, a dihydroxybenzene, or any mixture thereof; and

polymerizing the prepolymer to form polymer particles in gel form.

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

3. The method claim 1, 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.

4. The method of claim 3, wherein the polymer particles in gel form have a molar ratio of phenol to the first dihydroxybenzene of about 50:

1 to about 5;

1.

5. The method of claim 1, wherein the phenolic monomer comprises phenol, resorcinol, or a mixture thereof, and wherein the second catalyst comprises maleic anhydride, resorcinol, or a mixture thereof.

6. The method of claim 1, wherein about 50% or more of the polymer particles in gel form have an average cross-sectional length greater than or equal to 0.5 mm.

7. The method of claim 1, wherein the first catalyst comprises ammonia, dimethylethanolamine, ethylenediamine, triethylamine, trimethylamine, tripropylamine, diethylethanolamine, hexamethylenetetramine, lithium carbonate, or any mixture thereof.

8. The method of claim 1, wherein the carrier fluid comprises mineral oil, vegetable oil, or a mixture thereof.

9. The method of claim 1, wherein the carrier fluid has a viscosity of about 0.5 cP to about 400 cP at a temperature of 25°

C.

10. The method of claim 1, wherein the aldehyde monomer comprises formaldehyde.

11. The method of claim 1, wherein the prepolymer has a molar ratio of the phenolic monomer to the aldehyde monomer of about 0.1:

1 to about 1.5;

1.

12. The method of claim 1, wherein the emulsion or suspension polymerization comprises less than 1 wt % of any surfactant, based on the total weight of the carrier fluid.

13. The method of claim 1, wherein the polymer particles in gel form are made via the emulsion process, and wherein the emulsion process is an inverse emulsion process.

14. A method for making polymer particles in gel form via emulsion or suspension polymerization, the method 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, resorcinol, or a mixture thereof;

combining a carrier fluid and a second catalyst with the prepolymer to form an emulsion or a suspension, wherein the second catalyst comprises an anhydride, a dihydroxybenzene, or a mixture thereof; and

polymerizing the prepolymer in the emulsion or suspension to produce polymer particles in gel form.

15. The method of claim 14, wherein the first reaction mixture is reacted at a temperature of about 40°

C. to about 200°

C. to produce the prepolymer, and wherein the prepolymer is polymerized in the emulsion or suspension at a temperature of about 40°

C. to about 200°

C., and wherein the first catalyst comprises ammonia, dimethylethanolamine, ethylenediamine, triethylamine, trimethylamine, tripropylamine, diethylethanolamine, hexamethylenetetramine, lithium carbonate, or any mixture thereof.

16. The method of claim 14, wherein the first reaction mixture further comprises acetic acid, formic acid, nitric acid, citric acid, methane sulfonic acid, or any mixture thereof, and wherein the first reaction mixture has a pH of about 1 to about 5.

17. The method of claim 14, wherein the emulsion or suspension further comprises acetic acid, formic acid, nitric acid, citric acid, methane sulfonic acid, or any mixture thereof, and wherein the emulsion or suspension has a pH of about 1 to about 5.

18. A method for making an aerogel, comprising:

making a prepolymer from a first reaction mixture comprising a phenolic monomer, formaldehyde, and a first catalyst, wherein the phenolic monomer comprises phenol, a first dihydroxybenzene, or a mixture thereof, and wherein the first catalyst comprises ammonia, dimethylethanolamine, ethylenediamine, triethylamine, trimethylamine, tripropylamine, diethylethanolamine, hexamethylenetetramine, lithium carbonate, or any mixture thereof;

combining the prepolymer with a carrier fluid and a second catalyst comprising maleic anhydride, a second dihydroxybenzene, or a mixture a mixture thereof to form an emulsion or suspension;

polymerizing the prepolymer in the emulsion or suspension to form polymer particles in gel form, wherein about 40% or more of the polymer particles in gel form have an average cross-sectional length greater than or equal to 1 mm; and

drying the polymer particles in gel form to produce an aerogel.

19. The method of claim 18, wherein the carrier fluid comprises mineral oil, vegetable oil, or a mixture thereof, wherein the prepolymer has a molar ratio of the phenolic monomer to the aldehyde monomer of about 0.1:

1 to about 1.5;

1, wherein the prepolymer is polymerized in the emulsion to form the polymer particles in gel form, and wherein the emulsion is an inverse emulsion.

20. The method of claim 19, wherein the polymer particles in gel form are dried by supercritical extraction, freeze drying, air drying, or any combination thereof.