Phenothiazine based crosslinked polymer and methods thereof

Patent metadata

Field	Value
Publication number	US-11235306-B2
Application number	US-201916400433-A
Country	US
Kind code	B2
Filing date	May 1, 2019
Priority date	May 1, 2019
Publication date	Feb 1, 2022
Grant date	Feb 1, 2022

Abstract

Crosslinked polymers made up of polymerized units of phenothiazine, pyrrole, and aldehyde. The crosslinked polymers are porous with a BET surface area in the range of 300-600 m2/g. A method of synthesizing the crosslinked polymers is described. Processes for using the crosslinked polymers as adsorbent materials for adsorbing gases (e.g. CO2 capturing), and separating fluid mixtures under dry and wet conditions are also introduced.

First claim

The invention claimed is:

1. A crosslinked polymer, comprising reacted units of:
a phenothiazine monomer of formula (I)

or a salt thereof, a solvate thereof, a tautomer thereof a stereoisomer thereof, or a mixture thereof;
a pyrrole monomer of formula (II)

or a salt thereof, a solvate thereof, a tautomer thereof a stereoisomer thereof, or a mixture thereof; and
an aldehyde of formula (III)

or a salt thereof, a solvate thereof, a stereoisomer thereof, or a mixture thereof,
wherein:
R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are independently selected from the group consisting of a hydrogen, an optionally substituted alkyl, an optionally substituted cycloalkyl, an optionally substituted arylalkyl, an optionally substituted aryl, an optionally substituted alkoxy, and an optionally substituted alkylthio;
R 7 is selected from the group consisting of a hydrogen, an optionally substituted alkyl, an optionally substituted cycloalkyl, and an optionally substituted arylalkyl;
R 8 is selected from the group consisting of a hydrogen, an optionally substituted alkyl, an optionally substituted cycloalkyl, an optionally substituted arylalkyl, and an optionally substituted aryl; and
R 9 is selected from the group consisting of a hydrogen, an optionally substituted alkyl, an optionally substituted cycloalkyl, an optionally substituted arylalkyl, and an optionally substituted aryl.

2. The crosslinked polymer of claim 1 , wherein R 7 is a hydrogen.

3. The crosslinked polymer of claim 1 , wherein the phenothiazine monomer of formula (I) is

4. The crosslinked polymer of claim 1 , wherein the pyrrole monomer of formula (II) is

5. The crosslinked polymer of claim 1 , wherein the aldehyde of formula (III) is formaldehyde.

6. The crosslinked polymer of claim 1 , wherein a molar ratio of the pyrrole monomer of formula (II) to the phenothiazine monomer of formula (I) is in a range of 1:1 to 6:1.

7. The crosslinked polymer of claim 1 , wherein a molar ratio of the aldehyde of formula (III) to the phenothiazine monomer of formula (I) is in a range of 3:1 to 12:1.

8. The crosslinked polymer of claim 1 , wherein a molar ratio of the pyrrole monomer of formula (II) to the phenothiazine monomer of formula (I) is in a range of 2.5:1 to 3.5:1, and wherein a molar ratio of the aldehyde of formula (III) to the phenothiazine monomer of formula (I) is in a range of 5:1 to 7:1.

9. The crosslinked polymer of claim 1 , which has a BET surface area in the range of 300-600 m 2 /g.

10. The crosslinked polymer of claim 1 , which is porous with an average pore width of 0.8-2 nm.

11. The crosslinked polymer of claim 1 , which has a CO 2 uptake capacity in a range of 15-45 cm 3 /g at a temperature of 0-40° C. and a pressure of 400-800 Torr.

12. The crosslinked polymer of claim 1 , which has an ideal selectivity of CO 2 over N 2 in a range of 10-60.

13. A method of making the crosslinked polymer of claim 1 , the method comprising:
mixing the phenothiazine monomer of formula (I) and the aldehyde of formula (III) in a solution comprising a solvent to form a first mixture;
mixing the pyrrole monomer of formula (II) and an acid with the first mixture to form a second mixture; and
heating the second mixture thereby forming the crosslinked polymer.

14. The method of claim 13 , wherein the acid is ferric chloride.

15. The method of claim 13 , wherein the solvent comprises dimethylformamide.

16. The method of claim 13 , wherein the second mixture is heated at a temperature of 70-150° C.

17. A method of separating a first gas from a fluid mixture comprising the first gas and a second gas, the method comprising:
contacting the fluid mixture with the crosslinked polymer of claim 1 ; and
adsorbing the first gas onto the crosslinked polymer thereby separating the first gas from the fluid mixture and forming a first gas loaded crosslinked polymer.

18. The method of claim 17 , wherein the first gas is CO 2 , and wherein the second gas is N 2 .

19. The method of claim 17 , wherein the fluid mixture further comprises H 2 O.

20. The method of claim 18 , further comprising:
desorbing the first gas from the first gas loaded crosslinked polymer by flowing N 2 gas over the first gas loaded crosslinked polymer to regenerate the crosslinked polymer; and
reusing the crosslinked polymer.

Assignees

• Univ King Fahd Pet & Minerals

Inventors

• Al Hamouz Othman Charles Sadeq
• Abdelnaby Mahmoud Mohamed

Classifications

• B01J20/28064

  being in the range 500-1000 m2/g · CPC title

• B01J20/28061

  being in the range 100-500 m2/g · CPC title

• B01J20/3458

  in the gas phase · CPC title

• B01D2256/10

  Nitrogen · CPC title

• B01D2257/504

  Carbon dioxide · CPC title