Polystyrene sulfonate analogs and methods
View Patent ↗Provided are polystyrene sulfonate analogs and methods of making polystyrene sulfonate analogs. The polystyrene sulfonate analogs may be formed by a ring opening metathesis polymerization (ROMP). The ROMP may provide analogs having a precise periodicity. The polystyrene sulfonate analogs may have a relatively low glass transition temperature.
1. A polymer comprising repeat units according to Formula (B):
wherein R 1 -R 10 are independently selected from hydrogen, sulfonate, sulfonic acid, or a monovalent C 1 -C 10 hydrocarbyl,
at least one of R 1 -R 5 is sulfonate or sulfonic acid,
n and m independently are 1 to 10,000, and
wherein at least one of the repeat units comprising R 1 -R 5 is covalently bonded to at least one of the repeat units comprising R 6 -R 10 .
2. The polymer of claim 1 , wherein the polymer has a degree of sulfonation of about 1% to about 125%.
3. The polymer of claim 1 , wherein the polymer has a degree of sulfonation of about 80% to about 120%.
4. The polymer of claim 1 , wherein at least one of R 6 -R 10 is sulfonate or sulfonic acid, and the polymer has a degree of sulfonation of about 100% to about 120%.
5. The polymer of claim 1 , wherein the polymer has a glass transition temperature (T g ) of about 5° C. to about 145° C.
6. The polymer of claim 1 , wherein the polymer has a glass transition temperature (T g ) of about 10° C. to about 30° C.
7. The polymer of claim 1 , wherein the polymer is at least partially cross-linked.
8. A polymer consisting of repeat units according to Formula (A):
wherein, independently for each of the repeat units of Formula (A), R 1 -R 5 are independently selected from hydrogen, sulfonate, sulfonic acid, or a monovalent C 1 -C 10 hydrocarbyl,
at least one of R 1 -R 5 of at least one of the repeat units of Formula (A) is sulfonate or sulfonic acid, and
n is 200 to 10,000.
9. The polymer of claim 8 , wherein the polymer has a glass transition temperature (T g ) of about 5° C. to about 145° C.
10. The polymer of claim 8 , wherein the polymer has a glass transition temperature (T g ) of about 10° C. to about 30° C.
11. The polymer of claim 8 , wherein R 1 , R 2 , R 4 , and R 5 are hydrogen, and R 3 is sulfonate or sulfonic acid.
12. The polymer of claim 8 , wherein the polymer is at least partially cross-linked.
13. A method of making a polymer, the method comprising:
contacting a compound of formula (I) with a catalyst to form an unsaturated polymer by ring opening metathesis polymerization—
wherein R 11 -R 15 are independently selected from hydrogen or a monovalent C 1 -C 10 hydrocarbyl;
contacting the unsaturated polymer with a hydrogenation agent to form a saturated polymer;
contacting the saturated polymer with a sulfonating agent to form a saturated polymer substituted with sulfonic acid; and
optionally deprotonating the saturated polymer substituted with sulfonic acid to form a saturated sulfonated polymer.
14. The method of claim 13 , wherein the saturated polymer substituted with sulfonic acid or the saturated sulfonated polymer has a glass transition temperature (T g ) of about 5° C. to about 145° C.
15. The method of claim 13 , wherein the saturated polymer substituted with sulfonic acid or the saturated sulfonated polymer has a glass transition temperature (T g ) of about 10° C. to about 30° C.
16. The method of claim 13 , wherein, prior to the contacting of the saturated polymer with the sulfonating agent, the molar mass of the saturated polymer is about 45 kg/mol to about 160 kg/mol.
17. The method of claim 13 , wherein the saturated polymer substituted with sulfonic acid or the saturated sulfonated polymer has a degree of sulfonation of about 1% to about 125%.
18. The method of claim 13 , wherein the saturated polymer substituted with sulfonic acid or the saturated sulfonated polymer has a degree of sulfonation of about 80% to about 120%.
19. The method of claim 13 , further comprising at least partially cross-linking the unsaturated polymer prior to the contacting of the unsaturated polymer with the hydrogenation agent.