Versatile non-destructive surface modification of carbonaceous materials and process for grafting into polymer matrices

Patent metadata

Field	Value
Publication number	US-10316010-B2
Application number	US-201615383935-A
Country	US
Kind code	B2
Filing date	Dec 19, 2016
Priority date	Dec 17, 2015
Publication date	Jun 11, 2019
Grant date	Jun 11, 2019

Abstract

Disclosed is a non-destructive universal method of functionalization of graphitic carbonaceous materials that enables their alignment, cross-linking, and effective integration into composite materials.

First claim

We claim:

1. A non-destructive method of modifying the surface of carbonaceous materials comprising:
activating the surface of the carbonaceous materials; and
functionalizing the activated surface of the carbonaceous materials through treatment with a linker to create a [2+3] dipolar addition,
wherein the linker comprises a combination of (a) glycine, N-substituted glycine, or a combination thereof and (b) an aldehyde.

2. The method of claim 1 , wherein the activating the surface of the carbonaceous material is by way of treatment with at least one solvent, ultrasound, heat, microwave radiation, or combinations thereof.

3. The method of claim 2 , wherein activating the surface of the carbonaceous materials is by way of treatment of the materials with at least one solvent and ultrasound.

4. The method of claim 3 wherein ultrasound is applied at a frequency of between about 20,000 and about 100,000 Hz, at a power of between about 5 and about 1,000 watts per gallon, and for a duration of at least 10 minutes.

5. The method of claim 1 , wherein the linker further comprises a solvent.

6. The method of claim 1 , wherein the functionalization is achieved under heating, mechanical pressure, ultrasound, microwave radiation, or combinations thereof.

7. The method of claim 1 , further comprising a re-functionalization step.

8. The method of claim 1 , further comprising a step of adding a cross-linking reagent.

9. The method of claim 8 , wherein the cross-linking reagent is 1,6-di-(N-maleimido) hexane.

10. The method of claim 8 , wherein the cross-linking reagent is a diamine or polyamine, diol, or polyol.

11. The method of claim 8 , wherein the cross-linking reagent is a dicarboxylic acid.

12. A method of modifying the surface of carbonaceous materials comprising:
a. activating the surface of a plurality of carbon fibers by sonicating the carbon fibers in a solvent;
b. functionalizing the activated carbon fibers by heating in the solvent with 3-(acetylamino)propyl-aminoacetic acid and paraform; and
c. refunctionalizing the functionalized carbon fibers to produce amino-functionalized carbon fibers.

13. The method of claim 12 , wherein the refunctionalizing step comprises treating the functionalized carbon fibers with aqueous HCl, then with aqueous NaOH, and then with water.

14. The method of claim 12 , wherein the activated fibers are heated in the solvent to between about 50° C. and about 153° C. for at least one hour.

15. The method of claim 14 wherein the solvent is DMF.

16. A method of modifying the surface of carbonaceous materials comprising:
a. activating the surface of a plurality of carbon fibers by heating under a nitrogen atmosphere;
b. functionalizing the activated carbon fibers by heating in a solvent with 3 N-methylglycine and furfural; and
c. cross-linking the functionalized carbon fibers with a cross-linker.

17. The method of claim 16 wherein the cross-linker is 1,6-di-(N-maleimido)hexane.

18. The method of claim 16 , wherein the activation step a. provides sufficient heat to induce pyrolysis of the carbon fibers.

19. The method of claim 18 wherein the carbon fibers are heated to between about 100° C. and about 800° C.

Assignees

• South Dakota Board Of Regents

Inventors

• Sereda Grigoriy
• Keppen Joseph

Classifications

• C07C225/06

  and acyclic · CPC title

• C08K3/041

  Carbon nanotubes · CPC title

• C07F9/3813

  N-Phosphonomethylglycine; Salts or complexes thereof · CPC title

• C07D207/448

  with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide · CPC title

• C07C227/14

  from compounds containing already amino and carboxyl groups or derivatives thereof · CPC title