Polyamic acid, polyimide, and method for manufacturing graphite sheet

Patent metadata

Field	Value
Publication number	US-9593207-B2
Application number	US-201414172532-A
Country	US
Kind code	B2
Filing date	Feb 4, 2014
Priority date	Nov 13, 2013
Publication date	Mar 14, 2017
Grant date	Mar 14, 2017

Abstract

Disclosed is a method of fabricating a graphite sheet, including: polymerizing diamines and a dianhydride to form a polyamic acid. The polyamic acid is solvent casted on a substrate and hot baked to form a polyamic acid film or gel film. The polyamic acid film or gel film is biaxially stretched at a high temperature imidization or chemical imidization to form the polyimide film. The polyimide film is then carbonized and graphitized to form a graphite sheet. The diamines include a diamine of Formula 1 and a diamine of Formula 2, and the dianhydride includes a dianhydride of Formulae 3, Formula 4, Formula 5, Formula 6, Formula 7, Formula 8, Formula 9, or combinations thereof.

First claim

What is claimed is:

1. A method for manufacturing a graphite sheet, comprising:
performing a polymerization of diamines and a dianhydride to form a polyamic acid;
coating the polyamic acid on a substrate, and baking the coating to form a gel film;
biaxially stretching, thermally or chemically cyclizing and dehydrating the gel film to form a polyimide film; and
carbonizing and graphitizing the polyimide film to form a graphite sheet,
wherein the diamines include a diamine of Formula 1 and a diamine of Formula 2, and the dianhydride includes a dianhydride of Formula 3, Formula 4, Formula 5, Formula 6, Formula 7, Formula 8, Formula 9, or combinations thereof:

wherein the polyamic acid is formed by the polymerization of 1 part by mole of the dianhydride, a parts by mole of the diamine of Formula 1, and b parts by mole of the diamine of formula 2, wherein a+b=1, and 0.11≦a:b≦9.0.

2. A method for manufacturing a graphite sheet, comprising:
performing a polymerization of diamines and a dianhydride to form a polyamic acid;
coating the polyamic acid on a substrate, and baking the coating to form a gel film;
biaxially stretching, thermally or chemically cyclizing and dehydrating the gel film to form a polyimide film; and
carbonizing and graphitizing the polyimide film to form a graphite sheet,
wherein the diamines include a diamine of Formula 1 and a diamine of Formula 2, an additional diamine of Formula 10, Formula 11, Formula 12, Formula 13, Formula 14, Formula 15, Formula 16, Formula 17, Formula 18, Formula 19, Formula 20, Formula 21, or combinations thereof, and the dianhydride includes a dianhydride of Formula 3, Formula 4, Formula 5, Formula 6, Formula 7, Formula 8, Formula 9, or combinations thereof:

wherein the polyamic acid is formed by the polymerization of:
1 part by mole of the dianhydride;
a parts by mole of the diamine of Formula 1;
b parts by mole of the diamine of Formula 2; and
c parts by mole of the additional diamine of Formula 10, Formula 11, Formula 12, Formula 13, Formula 14, Formula 15, Formula 16, Formula 17, Formula 18, Formula 19, Formula 20, Formula 21, or combinations thereof,
wherein a+b+c=1, and 0.11≦a:b≦9.0;
wherein 0.1:0.9≦(a+b):c<1:0.

3. The method as claimed in claim 1 , wherein the step of graphitizing the polyimide film to form the graphite sheet is performed at a temperature of 2400° C. to 2800° C.

4. The method as claimed in claim 1 , further comprising adding a metal complex to the polymerization, and the dianhydride and the metal complex have a molar ratio of 1:0.001 to 1:0.2, wherein the metal complex includes a metal complex of Formula 22:

wherein each of R 1 and R 2 , being the same or different, is CH 3 or CF 3 ;
n is an integer of 2 to 4; and
M is Zr, Ni, TiO, Fe, Co, Mn, Mg, Cu, Al, Cr, Ba, Pr, Pd, Sc, Na, Zn, V, Y, Pt, or Tl.

5. The method as claimed in claim 4 , wherein M is Zr, R 1 is CH 3 , R 2 is CF 3 , and n=4.

6. The method as claimed in claim 4 , wherein M is Ni, R 1 is CH 3 , R 2 is CF 3 , and n=4.

7. The method as claimed in claim 4 , wherein M is TiO, R 1 is CH 3 , R 2 is CH 3 , and n=2.

8. The method as claimed in claim 4 , wherein M is Fe, R 1 is CH 3 , R 2 is CF 3 , and n=3.

9. The method as claimed in claim 4 , wherein the step of graphitizing the polyimide film to form the graphite sheet is performed at a temperature of 1800° C. to 2800° C.

10. The method as claimed in claim 2 , wherein the step of graphitizing the polyimide film to form the graphite sheet is performed at a temperature of 2400° C. to 2800° C.

11. The method as claimed in claim 2 , further comprising adding a metal complex to the polymerization, and the dianhydride and the metal complex have a molar ratio of 1:0.001 to 1:0.2, wherein the metal complex includes a metal complex of Formula 22:

wherein each of R 1 and R 2 , being the same or different, is CH 3 or CF 3 ;
n is an integer of 2 to 4; and
M is Zr, Ni, TiO, Fe, Co, Mn, Mg, Cu, Al, Cr, Ba, Pr, Pd, Sc, Na, Zn, V, Y, Pt, or Tl.

12. The method as claimed in claim 11 , wherein M is Zr, R 1 is CH 3 , R 2 is CF 3 , and n=4.

13. The method as claimed in claim 11 , wherein M is Ni, R 1 is CH 3 , R 2 is CF 3 , and n=4.

14. The method as claimed in claim 11 , wherein M is TiO, R 1 is CH 3 , R 2 is CH 3 , and n=2.

15. The method as claimed in claim 11 , wherein M is Fe, R 1 is CH 3 , R 2 is CF 3 , and n=3.

16. The method as claimed in claim 11 , wherein the step of graphitizing the polyimide film to form the graphite sheet is performed at a temperature of 1800° C. to 2800° C.

Assignees

• Ind Tech Res Inst

Inventors

• Hsiang Shou-Jui
• Chin Si-Yi
• Yang Wei-Ta

Classifications

• C08G73/14

  Polyamide-imides · CPC title

• C08G73/1067 Primary

  Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound · CPC title

• C01B32/205

  Preparation · CPC title

• C08G73/1071

  Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain · CPC title

• C01B32/20

  Graphite · CPC title