Plasticized melt spinning process using ionic liquids for production of polyacrylonitrile fibers

Patent metadata

Field	Value
Publication number	US-11795583-B2
Application number	US-202217580851-A
Country	US
Kind code	B2
Filing date	Jan 21, 2022
Priority date	Jan 21, 2021
Publication date	Oct 24, 2023
Grant date	Oct 24, 2023

Abstract

A method for producing polyacrylonitrile (PAN) fiber, the method comprising: (i) mixing PAN with an ionic liquid in which the PAN is soluble to produce a PAN composite melt in which the PAN is dissolved in the ionic liquid; (ii) melt spinning the PAN composite melt to produce the PAN fiber; and (iii) washing the PAN fiber with a solvent in which the ionic liquid is soluble to substantially remove the ionic liquid from the PAN fiber. Also described herein is a method for producing carbon fiber from the PAN fiber as produced above, the method comprising oxidatively stabilizing the PAN fiber produced in step (iii), followed by carbonizing the stabilized PAN fiber to produce the carbon fiber. The initially produced PAN fiber, stabilized PAN fiber, resulting carbon fiber, and articles made thereof are also described.

First claim

What is claimed is:

1. A method for producing polyacrylonitrile (PAN) fiber, the method comprising:
(i) mixing PAN with an ionic liquid in which the PAN is soluble to produce a PAN composite melt in which the PAN is dissolved in the ionic liquid, wherein the ionic liquid contains a counteranion that includes at least one nitrile group;
(ii) melt spinning the PAN composite melt to produce the PAN fiber; and
(iii) washing the PAN fiber with a solvent in which the ionic liquid is soluble to substantially remove the ionic liquid from the PAN fiber.

2. The method of claim 1 , wherein the ionic liquid does not contain chloride as anion.

3. The method of claim 1 , wherein the anion of the ionic liquid is dicyanamide.

4. The method of claim 1 , wherein the cation of the ionic liquid contains at least one nitrogen atom.

5. The method of claim 1 , wherein the cation of the ionic liquid comprises at least one ring containing at least one ring nitrogen atom.

6. The method of claim 1 , wherein the cation of the ionic liquid contains at least one nitrile group.

7. The method of claim 1 , wherein the cation of the ionic liquid comprises an imidazolium ring.

8. The method of claim 7 , wherein the ionic liquid has the following structure:

wherein: R 1 and R 2 are independently a saturated or unsaturated, straight-chained, branched, or cyclic hydrocarbon group (R) having 1-10 carbon atoms and optionally containing one or more heteroatoms selected from oxygen, nitrogen, sulfur, and fluorine atoms; R 3 is selected from hydrogen atom and R; and X is a counteranion that includes at least one nitrile group.

9. The method of claim 8 , wherein R 3 is hydrogen atom.

10. The method of claim 8 , wherein X − is not chloride.

11. The method of claim 8 , wherein X − is dicyanamide.

12. The method of claim 1 , wherein the solvent is aqueous based.

13. The method of claim 12 , wherein the solvent is deionized water.

14. The method of claim 1 , wherein the ionic liquid is present in a greater amount by weight than the PAN in step (i).

15. A method for producing a carbon fiber, the method comprising:
(i) mixing PAN with an ionic liquid in which the PAN is soluble to produce a PAN composite melt in which the PAN is dissolved in the ionic liquid, wherein the ionic liquid contains a counteranion that includes at least one nitrile group;
(ii) melt spinning the PAN composite melt to produce the PAN fiber;
(iii) washing the PAN fiber with a solvent in which the ionic liquid is soluble to substantially remove the ionic liquid from the PAN fiber;
(iv) oxidatively stabilizing the PAN fiber produced in step (iii); and
(v) carbonizing the PAN fiber produced in step (iv) to produce said carbon fiber.

16. The method of claim 15 , further comprising: (vi) subjecting the carbon fiber to graphitization.

17. The method of claim 15 , wherein the ionic liquid does not contain chloride as anion.

18. The method of claim 15 , wherein the anion of the ionic liquid is dicyanamide.

19. The method of claim 15 , wherein the cation of the ionic liquid contains at least one nitrogen atom.

20. The method of claim 15 , wherein the cation of the ionic liquid comprises at least one ring containing at least one ring nitrogen atom.

21. The method of claim 15 , wherein the cation of the ionic liquid contains at least one nitrile group.

22. The method of claim 15 , wherein the cation of the ionic liquid comprises an imidazolium ring.

23. The method of claim 22 , wherein the ionic liquid has the following structure:

wherein: R 1 and R 2 are independently a saturated or unsaturated, straight-chained, branched, or cyclic hydrocarbon group (R) having 1-10 carbon atoms and optionally containing one or more heteroatoms selected from oxygen, nitrogen, sulfur, and fluorine atoms; R 3 is selected from hydrogen atom and R; and X − is a counteranion that includes at least one nitrile group.

24. The method of claim 1 , further comprising: (iv) separating the removed ionic liquid from the solvent and re-using the removed ionic liquid in step (i).

Assignees

• Ut Battelle Llc
• Univ Tennessee Res Found

Inventors

• Dai Sheng
• Luo Huimin
• Martin Halie J

Classifications

• D01F6/54 Primary

  of polymers of unsaturated nitriles · CPC title

• D01D5/10

  using organic materials · CPC title

• D01F9/225

  from stabilised polyacrylonitriles · CPC title

• D10B2321/10

  polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide · CPC title

• D01F6/18 Primary

  from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide · CPC title