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

Patent metadata

Field	Value
Publication number	US-9133295-B2
Application number	US-201314092267-A
Country	US
Kind code	B2
Filing date	Nov 27, 2013
Priority date	Nov 29, 2012
Publication date	Sep 15, 2015
Grant date	Sep 15, 2015

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.

First claim

What is claimed is:

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.

Assignees

• Georgia Pacific Chemicals Llc

Inventors

• Qureshi Shahid P
• Dong Xing
• Chan Charles C
• Ludvik Joseph Frank

Classifications

• C08G8/10

  with phenol · CPC title

• C08G8/22

  Resorcinol · CPC title

• C08J2205/02

  the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition · CPC title

• C08G85/004

  Modification of polymers by chemical after-treatment · CPC title

• C08G8/32 Primary

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