Method for depositing a fluorocarbonsulfonic acid polymer on a support from a solution

• US 4,661,411 A
• Filed: 02/25/1986
• Issued: 04/28/1987
• Est. Priority Date: 02/25/1986
• Status: Expired due to Fees

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Weaver, John D., Martin, Charles W., Ezzell, Bobby R.
• Primary Examiner(s): Page, Thurman K.
• Application Number:
  US06/832,627
• Time in Patent Office: 427 Days
• Field of Search: 502/402, 502/109, 502/4, 502/8, 502/439, 427/230, 427/232, 427/385.5, 427/393.6, 427/389.7, 427/388.1, 427/435, 427/430.1, 427/443.2, 428/421
• US Class Current: 428/421
• CPC Class Codes: B01J 2231/32 Addition reactions to C=C or C-C triple bonds
• CPC Class Codes: B01J 2231/323 Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
• CPC Class Codes: B01J 2231/4205 C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
• CPC Class Codes: B01J 2231/52 Isomerisation reactions
• CPC Class Codes: B01J 31/10 sulfonated
• CPC Class Codes: B01J 37/0203 the impregnation liquid containing organic compounds
• CPC Class Codes: C08F 214/262 with fluorinated vinyl ethers
• CPC Class Codes: C08F 6/12 Separation of polymers from solutions
• CPC Class Codes: C08F 8/00 Chemical modification by after-treatment graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers

Abstract

This invention discloses improved heterogeneous acid catalysts and a method for preparing these catalysts. A heterogeneous acid catalyst has been prepared by treating a carrier material with a solution containing a fluorocarbonsulfonic acid polymer dissolved in a suitable solvent, removing the solvent, and heat treating the coated carrier in such a way so as to prevent the polymer from being leached off the carrier. The final heat treatment of the composition to prevent the polymer from redissolving comprises an improvement in the preparation of a heterogeneous catalyst.

Claims

1. The method of supporting a fluorinated polymer having pendant chains containing sulfonic acid groups, on a support, comprising the steps:

(a) soaking a substrate with a solution that contains a fluorinated polymer having pendant chains containing sulfonic acid groups;

(b) removing the solvent from the mixture;

(c) heating the remaining composition to above the glass transition temperature of the polymer for a sufficient time to render the polymer insoluble.

2. The method of claim 1 wherein the temperature is above 100°

C.

3. The method of claim 1 wherein the temperature is between 150°

C. and 300°

C.

4. The method of claim 1 wherein the temperature is between 200°

C. and 225°

C.

5. The method of claim 1 wherein the temperature is about 225°

C.

6. The method of claim 1 wherein the solution that is used to soak the support contains a fluorinated polymer having pendant chains with the structure:

##STR3## where Z is F, Cl, Br, CF₃, CF₂ Cl, or fluorinated alkyl;

m is 0 to 4;

d is 2 to 5.

7. The method of claim 6 wherein m is 0 and d is 2.

8. The method of claim 1 wherein the solvent is an alcohol or a mixture of an alcohol and water

9. The method of claim 8 wherein the alcohol is ethanol.

10. The method of claim 1 wherein the dissolved polymer passes through a 0.2 micrometer filter.

11. The method of claim 1 wherein the support is resistant to the sulfonic acid polymer solution and to the temperature to which it is heated.

12. The method of claim 11 wherein the support is alumina, silica, zeolites, silicon carbide, silica-alumina, porous glass, ceramic, spinel, clay, or carbon.

13. The product prepared by the method of claim 1.

14. The process of using the product prepared by the method of claim 1 as an acid catalyst.