Biobased carbon fibers and carbon black and methods of making the same

Patent metadata

Field	Value
Publication number	US-10899622-B2
Application number	US-201815950850-A
Country	US
Kind code	B2
Filing date	Apr 11, 2018
Priority date	Jun 30, 2017
Publication date	Jan 26, 2021
Grant date	Jan 26, 2021

Abstract

Bio-based materials, e.g., epoxide starting material, a beta-lactone starting material and/or a beta-hydroxy amide starting material, may be used as feedstocks in processes for making and using acrylonitrile and acrylonitrile derivatives to produce, among other products, carbon fibers and carbon black.

First claim

What is claimed is:

1. A method of producing a carbon fiber material, the method comprising:
a. forming acrylonitrile from at least one of an epoxide or carbon monoxide starting material that is derived from a bio-based and/or renewable source;
b. polymerizing the acrylonitrile to produce a polyacrylonitrile precursor;
c. thermally stabilizing the polyacrylonitrile precursor to afford thermally stabilized carbon fibers; and
d. carbonizing the thermally stabilized carbon fibers to produce the carbon fiber material.

2. The method from claim 1 , wherein the acrylonitrile is produced by a process comprising:
a. introducing the at least one of bio-based and/or renewable sourced epoxide and carbon monoxide starting materials to at least one reaction vessel through at least one feed stream inlet;
b. contacting the at least one of bio-based and/or renewable sourced epoxide and carbon monoxide starting materials with a carbonylation catalyst in the at least one reaction vessel to produce a beta-lactone intermediate;
c. contacting the beta-lactone intermediate with a heterogenous catalyst to produce an organic acid product; and
d. reacting the organic acid product with an ammonia reagent under ammoxidation conditions in the at least one reaction vessel to produce the acrylonitrile product.

3. The method from claim 1 , wherein the polyacrylonitrile precursor comprises polyacrylonitrile fibers produced by wet or dry-jet-wet spinning of an acrylonitrile monomer or copolymer.

4. The method from claim 1 , wherein the polyacrylonitrile precursor is thermally stabilized by controlled low-temperature heating over the range 200-300° C. in air.

5. The method from claim 1 , wherein the carbon fiber material is surface treated to afford a carbon fiber composite.

6. The method from claim 1 , wherein the thermally stabilized carbon fibers are carbonized at a carbonization temperature over a range of 1,500-1,600° C.

7. The method from claim 6 , wherein the thermally stabilized carbon fibers are additionally heat-treated above 1,600° C. and up to 3,000° C. to afford a graphitized carbon fiber material.

8. The process from claim 3 , wherein the polyacrylonitrile precursor further comprises carbon black byproduct, the carbon black byproduct mechanically removed from the polyacrylonitrile precursor by performing at least one of heating, stretching and/or polishing the polyacrylonitrile precursor.

9. The process from claim 2 , wherein the process further comprises the steps: polymerizing the beta-lactone intermediate with a polymerization initiator in the at least one reaction vessel to produce a polylactone product; and heating the polylactone product under thermolysis conditions in the at least one reaction vessel to produce the organic acid product.

10. The method from claim 1 , wherein the acrylonitrile is produced by a process comprising:
a. introducing the at least one of bio-based and/or renewable sourced epoxide and carbon monoxide starting materials to at least one reaction vessel through at least one feed stream inlet;
b. contacting the at least one of bio-based and/or renewable sourced epoxide and carbon monoxide starting materials with a carbonylation catalyst in the at least one reaction vessel to produce a beta-lactone intermediate;
c. contacting the beta-lactone intermediate with a heterogenous catalyst to produce an organic acid product;
d. reacting the organic acid product with an alcohol reagent in the at least one reaction vessel to produce an ester product; and
e. reacting the ester product with an ammonia reagent under ammoxidation conditions in the at least one reaction vessel to produce the acrylonitrile product.

11. The method of claim 1 , wherein the acrylonitrile has a formula (3):

wherein R 1 is H or alkyl,
or isomers thereof, the acrylonitrile produced by a method comprising:
combining a compound of formula (2) with a dehydration agent to produce the compound of formula (3), or isomers thereof, wherein:
the compound of formula (2) is

wherein R 1 is as defined above for formula (3),

and

the dehydration agent comprises phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, or an aluminum complex, or any combination thereof.

12. The method of claim 11 , further comprising combining a compound of formula (1) with ammonia to produce the compound of formula (2), wherein:
the compound of formula (1) is

13. The method of claim 12 , wherein the ammonia is ammonium hydroxide or aqueous ammonia.

14. The method of claim 11 , wherein the dehydration agent comprises an organophosphorous compound selected from the group consisting of ethyl dichlorophosphate, diethyl chlorophosphate, methyl dichlorophosphate, dimethyl chlorophosphate, ethyl difluorophosphate, diethyl fluorophosphate, methyl difluorophosphate, and dimethyl fluorophosphate, or any combination thereof.

15. The method of claim 11 , wherein the dehydration agent comprises a carbodiimide compound having a formula R 4 —N═C═N—R 5 , wherein each R 4 and R 5 is independently alkyl or cycloalkyl.

16. The method of claim 15 , wherein the carbodiimide compound is N, N′-dicyclohexylcarbodiimide.

17. The method of claim 11 , wherein the dehydration agent comprises a triazine compound that is a halo-substituted triazine compound.

18. The method of claim 17 , wherein the triazine compound is 1,3,5-triazine or cyanuric chloride.

19. The method of claim 11 , wherein the dehydration agent comprises an organosilicon compound that is a silazane or a silane.

20. The method of claim 19 , wherein the silane is bis(trimethylsilyl)amine.

21. The method of claim 11 , wherein the dehydration agent comprises an organosilicon compound that is a hydrosilane, and an alkylammonium halide.

22. The method of claim 21 , wherein the alkylammonium halide is tetrabutylammonium fluoride.

23. The method of claim 11 , wherein the dehydration agent comprises a transition metal complex further comprising at least one halide or oxide ligand.

24. The method of claim 23 , wherein the transition metal complex comprises a compound selected from the group consisting of palladium chloride, zinc chloride and vanadium oxide.

25. The method of claim 11 , wherein the dehydration agent comprises an organosilicon compound and a transition metal complex.

26. The method of claim 11 , wherein the dehydration agent comprises: (i) zinc triflate and N-methyl-N-(trimethylsilyl)trifluoroacetamide; or (ii) copper chloride and N-methyl-N-(trimethylsilyl)trifluoroacetamide; or (iii) an iron complex and a silane; or (iv) iron carbonate and diethoxymethylsilane.

27. The method of claim 11 , wherein the dehydration agent comprises an aluminum complex that comprises AlCl 3 ·H 2 O/KI/H 2 )/CH 3 CN.

28. The process from claim 9 , wherein the polymerization initiator comprises a compound having the general formula of M″X where

Assignees

• Novomer Inc

Inventors

• Sookraj Sadesh
• Munsterman Herb
• Lee Han

Classifications

• C08F120/44 Primary

  Acrylonitrile · CPC title

• C09C1/56

  Treatment of carbon black {; Purification} · CPC title

• C09C3/12

  Treatment with organosilicon compounds {(C09C3/006 takes precedence)} · CPC title

• C09C1/48

  Carbon black · CPC title

• C09C1/44

  Carbon · CPC title