Fluorinated-aliphatic hydrocarbon based stable anion-exchange membrane and its method of preparation thereof

Patent metadata

Field	Value
Publication number	US-12227626-B2
Application number	US-202017622185-A
Country	US
Kind code	B2
Filing date	Jun 25, 2020
Priority date	Jun 25, 2019
Publication date	Feb 18, 2025
Grant date	Feb 18, 2025

Abstract

Anion-exchange membranes are useful for electro-membrane processes such as electrodialysis (water desalination, separation of inorganics from organic molecules, separation of specific inorganic ion, etc.), in-situ ion-exchange and ion substitution, electro-deionization for producing ultrapure water, polymer electrolyte membrane for alkaline fuel cell and electrolysis applications. The present invention discloses an acid and base resistant fluorinated hydrocarbon based anion-exchange membrane and its method of preparation thereof. In the first step co-polymerization is carried out between N-isopropylacrylamide and 1-vinylimidazole. In the second step, obtained inter-polymer of isopropylacrylamide-co-vinylimidazole co-polymer is mixed with poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP) (IA-co-VI/PVDF-co-HFP), which is used for casting membrane film of desired thickness. The obtained casted membrane thin film is quaternized in methyl iodide solution.

First claim

We claim:

1. An anion-exchange membrane having repeating unit of Formula 1,

wherein m and n are integers.

2. The anion-exchange membrane of claim 1 , wherein the membrane has an ion-exchange capacity in the range of 1.00 to 1.70 meq/g.

3. The anion-exchange membrane of claim 1 , wherein the membrane has conductivity in the range of 3.0×10 −2 to 6.0×10 −2 S cm −1 .

4. The anion-exchange membrane of claim 1 , wherein the membrane exhibits a swelling ratio in the range of 5-10% under treatment of water at a temperature in the range of 60-65° C. for a time period in the range of 24-36 hours.

5. The anion-exchange membrane of claim 1 , wherein a membrane weight, an ion-exchange capacity and a conductivity loss is less than 4% under an alkaline environment or under a harassed oxidative environment.

6. The anion-exchange membrane of claim 5 , wherein the alkaline environment is achieved by 2.0 M NaOH at a temperature in the range of 60-65° C. for a time period in the range of 120-150 hours; and the harassed oxidative environment is achieved by 3 ppm+3% H 2 O 2 at temperature of 70° C. for 1-3 hours.

7. A process for the preparation of the anion-exchange membrane of claim 1 , comprising the steps of:
i. adding 1-vinylimidazole and N-isopropylacrylamide to dimethyl acetamide in a vessel under constant stirring and nitrogen environment at temperature in the range of 25 to 30° C. to obtain a solution;
ii. charging the solution obtained in step (i) with radical initiator azobisisobutyronitrile (AIBN) at temperature in the range of 90-95° C. for period in the range of 24 hours with stirring to obtain an isopropylacrylamide-co-vinylimidazole (IA-co-VI) copolymer solution;
iii. mixing a poly(vinylidene fluoride-co-hexafluoropropylene) [PVDF-co-HFP] copolymer and dimethyl acetamide (DMAc) in a ratio of 1:5 (w/v) for time period in the range of 14 hours to obtain a solution;
iv. mixing the solutions obtained in steps (ii) and (iii) with stirring at a temperature in the range of 75-95° C. for a time period of 12 hours to obtain a membrane forming polymer solution;
v. casting a thin film membrane with the membrane forming polymer solution obtained in step (iv), followed by drying at a temperature in the range of 60-80° C. for a time period in the range of 24-30 hours under vacuum to obtain a membrane;
vi. quaternizing the thin film membrane obtained in step (v) by dipping the thin film membrane in a 10 wt % methyl iodide solution for a time period in the range of 24-30 hours at a temperature in the range of 30-40° C. to introduce a quaternary ammonium group in a matrix of the thin film membrane to form a quaternized thin film membrane; and
vii. washing the quaternized thin film membrane obtained in step (vi) followed by immersing the quaternized thin film membrane in a sodium hydroxide solution to obtain the anion-exchange membrane.

8. The process of claim 7 , wherein in the step (i), the N-isopropylacrylamide and the 1-vinylimidazole are added in a weight ration ranging from 2:0.5 to 2:1.5.

9. The process of claim 7 , wherein in step (iv), the dimethyl acetamide and the isopropylacrylamide-co-vinylimidazole copolymer in the ratio of 1:10 (w/v).

10. The process of claim 7 , wherein in step (iv), the ratio of isopropylacrylamide-co-vinylimidazole (IA-co-VI) copolymer and PVDF-co-HFP copolymer is in the range of 1.0-1.5:0.5-0.7 (w/w).

11. The anion-exchange membrane of claim 1 , wherein the structure

of Formula 1 is formed by
preparing an isopropylacrylamide-co-vinylimidazole copolymer from N-isopropylacrylamide and 1-vinylimidazole in a weight ratio ranging from 2:0.5 to 2:1.5; and
reacting vinylimidazole groups of the isopropylacrylamide-co-vinylimidazole copolymer with methyl iodide to form vinyl-3-methylimidazolium groups.

12. An anion-exchange membrane comprising:
an isopropylacrylamide-co-vinyl-3-methylimidazolium copolymer; and
a poly (vinylidene fluoride-co-hexafluoropropylene) copolymer,
wherein the isopropylacrylamide-co-vinyl-3-methylimidazolium copolymer and the poly(vinylidene fluoride-co-hexafluoropropylene) copolymer are bound together by hydrogen bonding interactions.

13. The anion-exchange membrane of claim 12 , wherein the membrane has an ion-exchange capacity in the range of 1.00 to 1.70 meq/g.

14. The anion-exchange membrane of claim 12 , wherein the membrane has conductivity in the range of 3.0×10 −2 to 6.0×10 −2 S cm −1 .

15. The anion-exchange membrane of claim 12 , wherein the membrane exhibits a swelling ratio in the range of 5-10% under treatment of water at a temperature in the range of 60-65° C. for a time period in the range of 24-36 hours.

16. The anion-exchange membrane of claim 12 , wherein a membrane weight, an ion-exchange capacity and a conductivity loss is less than 4% under an alkaline environment or under a harassed oxidative environment.

17. The anion-exchange membrane of claim 16 , wherein the alkaline environment is achieved by 2.0 M NaOH at a temperature in the range of 60-65° C. for a time period in the range of 120-150 hours; and the harassed oxidative environment is achieved by 3 ppm+3% H 2 O 2 at temperature of 70° C. for 1-3 hours.

Assignees

• Council Scient Ind Res
• Ongc Energy Centre

Inventors

• Shukla Geetanjali
• Bhushan Mani
• Kumar Sonu
• Das Arindam Kumar
• Sharma Prerana
• Singh Anuj Kumar
• Shahi Vinod Kumar
• Bhargava Bharat
• Parvatalu Damaraju

Classifications

• C08J2427/16

  Homopolymers or copolymers of vinylidene fluoride · CPC title

• C08J2333/26

  Homopolymers or copolymers of acrylamide or methacrylamide · CPC title

• Y02E60/50

  Fuel cells · CPC title

• C08J5/2237 Primary

  containing fluorine · CPC title