Polymeric acid catalysts and uses thereof

• US 10,131,721 B2
• Filed: 06/03/2015
• Issued: 11/20/2018
• Est. Priority Date: 02/28/2011
• Status: Active Grant

• Current Assignee: DSM Nutritional Products Incorporated (DSM-Firmenich AG)
• Original Assignee: Cadena Bio Inc. (Kaleido Biosciences Inc)
• Inventors: Geremia, John M., Baynes, Brian M., Dhawan, Ashish
• Primary Examiner(s): Cai, Wenwen
• Application Number:
  US14/730,143
• Publication Number:
  US 20160122447A1
• Time in Patent Office: 1,266 Days
• Field of Search: 526258
• CPC Class Codes: B01J 31/06 containing polymers organometallic polymers B01J31/123; polymer-bound organometallic complexes B01J31/165; coordination polymers B01J31/1691
• CPC Class Codes: C08F 12/18 Chlorine
• CPC Class Codes: C08F 212/08 Styrene
• CPC Class Codes: C08F 212/18 Chlorine
• CPC Class Codes: C08F 212/22 Oxygen
• CPC Class Codes: C08F 212/30 Sulfur
• CPC Class Codes: C08F 212/36 Divinylbenzene
• CPC Class Codes: C08F 226/06 by a heterocyclic ring containing nitrogen
• CPC Class Codes: C08F 226/08 N-Vinyl-pyrrolidine
• CPC Class Codes: C08F 8/24 Haloalkylation
• CPC Class Codes: C08F 8/30 Introducing nitrogen atoms or nitrogen-containing groups
• CPC Class Codes: C08F 8/32 by reaction with amines
• CPC Class Codes: C08F 8/36 Sulfonation; Sulfation
• CPC Class Codes: C08F 8/40 Introducing phosphorus atoms or phosphorus-containing groups
• CPC Class Codes: C08F 8/42 Introducing metal atoms or metal-containing groups
• CPC Class Codes: C08F 8/44 Preparation of metal salts or ammonium salts
• CPC Class Codes: C08G 8/28 Chemically modified polycondensates
• CPC Class Codes: C08H 8/00 Macromolecular compounds derived from lignocellulosic materials pretreatment thereof B27N
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel

Abstract

Polymers including acidic monomers and ionic monomers connected to form a polymeric backbone are disclosed. The polymers may also include, e.g., acidic-ionic monomers within the polymeric backbone. Each acidic monomer may independently include at least one Bronsted-Lowry acid, and each ionic monomer may independently include at least one nitrogen-containing cationic group or phosphorous-containing cationic group. The acidic monomers and ionic monomers may make up, e.g., at least about 30% of the monomers of the polymer, based on the ratio of the number of acidic monomers and ionic monomers to the total number of monomers present in the polymer. The total number of ionic monomers may, e.g., exceed the total number of acidic monomers in the polymer. The polymer may be substantially insoluble in water.

Claims

1. A polymer comprising acidic monomers, ionic monomers, and acidic-ionic monomers connected to form a polymeric backbone,

wherein each acidic monomer independently comprises at least one Bronsted-Lowry acid,

wherein each ionic monomer independently comprises at least one nitrogen-containing cationic group or phosphorous-containing cationic group,

wherein each acidic-ionic monomer independently comprises at least one Bronsted-Lowry acid and at least one cationic group,

wherein the acidic monomers and ionic monomers

make up at least about 30% of the monomers of the polymer, based on the ratio of the number of acidic monomers and ionic monomers to the total number of monomers present in the polymer;

and

wherein the polymer is substantially insoluble in water.

2. The polymer of claim 1, wherein the Bronsted-Lowry acid at each occurrence is independently selected from the group consisting of sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, boronic acid, and perfluorinated acid.

3. The polymer of claim 1, wherein one or more of the acidic monomers each further comprise a linker connecting the Bronsted-Lowry acid to the polymeric backbone.

4. The polymer of claim 3, wherein the linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate.

5. The polymer of claim 1, wherein the nitrogen-containing cationic group at each occurrence is independently selected from the group consisting of pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyradizinium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.

6. The polymer of claim 1, wherein the phosphorous-containing cationic group at each occurrence is independently selected from the group consisting of triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.

7. The polymer of claim 1, wherein one or more of the ionic monomers each further comprise a linker connecting the nitrogen-containing cationic group or the phosphorous-containing cationic group to the polymeric backbone.

8. The polymer of claim 7, wherein the linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate.

9. The polymer of claim 1, wherein the acidic monomers and ionic monomers make up at least about 50% of the monomers of the polymer, based on the ratio of the number of acidic monomers and ionic monomers to the total number of monomers present in the polymer.

10. A polymer comprising acidic monomers and ionic monomers connected to form a polymeric backbone,

wherein each acidic monomer independently comprises at least one Bronsted-Lowry acid,

wherein each ionic monomer independently comprises at least one nitrogen-containing cationic group or phosphorous-containing cationic group, and

wherein the total number of ionic monomers exceeds the total number of acidic monomers in the polymer.

11. The polymer of claim 10, wherein the Bronsted-Lowry acid at each occurrence is independently selected from the group consisting of sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, boronic acid, and perfluorinated acid.

12. The polymer of claim 10, wherein one or more of the acidic monomers each further comprise a linker connecting the Bronsted-Lowry acid to the polymeric backbone.

13. The polymer of claim 12, wherein the linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate.

14. The polymer of claim 10, wherein the nitrogen-containing cationic group at each occurrence is independently selected from the group consisting of pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyradizinium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.

15. The polymer of claim 10, wherein the phosphorous-containing cationic group at each occurrence is independently selected from the group consisting of triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.

16. The polymer of claim 10, wherein one or more of the ionic monomers each further comprise a linker connecting the nitrogen-containing cationic group or the phosphorous-containing cationic group to the polymeric backbone.

17. The polymer of claim 16, wherein the linker at each occurrence is independently selected from the group consisting of unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate.

18. The polymer of claim 10, wherein the polymer further comprises acidic-ionic monomers connected to form the polymeric backbone.

19. The polymer of claim 10, wherein the total number of ionic monomers is at least 2 times the total number of acidic monomers in the polymer.