Polymeric acid catalysts and uses thereof
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.
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.