Multifunctional crosslinking agent, crosslinked polymer, and method of making same

Patent metadata

Field	Value
Publication number	US-10294255-B1
Application number	US-201615009360-A
Country	US
Kind code	B1
Filing date	Jan 28, 2016
Priority date	Aug 7, 2015
Publication date	May 21, 2019
Grant date	May 21, 2019

Abstract

A multifunctional crosslinking agent, a crosslinked polymer, and a method of making the same are disclosed. The multifunctional crosslinking agent, which may be used to crosslink amine-terminated polyamides, polyimides, or poly(amide-imide)s, includes three or four anhydride functional groups. The multifunctional crosslinking agent may be defined by a general chemical formula (I): (Z—Ar—) n —W, wherein W represents an anhydride functional group that is directly or indirectly bonded to Ar; Ar represents an aryl group that is directly bonded to W; and n is equal to 3 when W is P═O or N, or n is equal to 4 when W is Si or a carbon moiety.

First claim

What is claimed is:

1. A multifunctional crosslinking agent comprising a plurality of anhydride functional groups, and defined by a chemical formula (I):
(Z—Ar) n —W  (I)

wherein Z represents an anhydride functional group that is directly bonded to Ar;
Ar represents an aryl-ether group that is directly bonded to W; and
n is equal to 3 when W is P═O or N, or n is equal to 4 when W is Si or a carbon moiety.

2. The multifunctional crosslinking agent of claim 1 , wherein W is P═O.

3. The multifunctional crosslinking agent of claim 1 , wherein W is N.

4. The multifunctional crosslinking agent of claim 1 , wherein W is the carbon moiety.

5. The multifunctional crosslinking agent of claim 1 , wherein W is Si.

6. The multifunctional crosslinking agent of claim 1 , wherein Ar is an oxyphenylene group (—OPh-) that is para- or meta-substituted with respect to oxygen, and the agent is further defined by a formula (II):
(Z—OPh) n -W.

7. The multifunctional crosslinking agent of claim 1 , wherein Z is an aromatic anhydride.

8. The multifunctional crosslinking agent of claim 7 , wherein the aromatic anhydride is a phthalic anhydride or a naphthalic anhydride.

9. The multifunctional crosslinking agent of claim 1 , wherein Ar is an oxyphenylene group (—OPh-) that is para- or meta-substituted with respect to oxygen, and wherein Z is a phthalic anhydride group that is connected to the oxyphenylene group through an ether bond.

10. The multifunctional crosslinking agent of claim 1 , wherein W is P═O, wherein Ar is an oxyphenylene group (—OPh-) that is para- or meta-substituted with respect to oxygen, and wherein the agent is further defined by a formula (III):
(Z—OPh) 3 -P═O.

11. The multifunctional crosslinking agent of claim 10 , wherein Z is a phthalic anhydride group that is connected to the oxyphenylene group through the ether bond, and wherein the agent is further defined by a formula (IV):

wherein R 1 through R 8 are independently selected from H or C1-C4 alkyl.

12. The multifunctional crosslinking agent of claim 11 , wherein the agent is selected from tris[3-(3,4-dicarboxyphenoxy)phenyl]phosphine oxide trianhydride or tris[4-(3,4-dicarboxyphenoxy)phenyl]phosphine oxide trianhydride.

13. The multifunctional crosslinking agent of claim 1 , wherein W is N, wherein Ar is an oxyphenylene group (—OPh-) that is para- or meta-substituted with respect to oxygen, and wherein the agent is further defined by a general formula (V):
(Z—OPh) 3 -N.

14. The multifunctional crosslinking agent of claim 13 , wherein Z is a phthalic anhydride group that is connected to the oxyphenylene group through the ether bond, and wherein the agent is further defined by a general formula (VI):

wherein R 1 through R 8 are independently selected from H or C1-C4 alkyl.

15. The multifunctional crosslinking agent of claim 14 , wherein the agent is selected from tris[3-(3,4-dicarboxyphenoxy)phenyl]amine trianhydride or tris[4-(3,4-dicarboxyphenoxy)phenyl]amine trianhydride.

16. A crosslinked polymer composition comprising an amino-terminated polymer selected from a polyamide, a polyimide, a poly(amide-imide), or mixtures thereof, which is cross-linked by the multifunctional cross-linking agent of claim 1 .

17. The crosslinked polymer composition of claim 16 , wherein the polyamide is a polymerization reaction product of a diamine with a dicarboxylic acid, a diacid halide, or a combination thereof; and wherein the diamine is reacted in a stoichiometric excess relative to the dicarboxylic acid, the diacid halide, or a sum total of the combination thereof.

18. The crosslinked polymer composition of claim 16 , wherein the polyimide is a polymerization reaction product of a diamine with a dianhydride; and wherein the diamine is reacted in a stoichiometric excess relative to the dianhydride.

19. The crosslinked polymer composition of claim 16 , wherein the polyimide is a polymerization reaction product of a diamine with
1) a trimellitic anhydride, a diacid derivative of trimellitic acid, or trimellitic acid, or
2) a dianhydride, and a dicarboxylic acid, a diacid halide, or a combination thereof; and wherein the diamine is reacted in a stoichiometric excess relative to a sum total of 1) or 2).

20. The crosslinked polymer composition of claim 16 , wherein the poly(amide-imide) is a polymerization reaction product of a diamine with 1) diimide-dicarboxylic acid monomer, and/or 2) a diamide-dianhydride monomer.

Assignees

• Us Air Force

Inventors

• Tan Loon-Seng
• Wang David Huabin

Classifications

• C08G73/1071

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

• C07D307/89

  with two oxygen atoms directly attached in positions 1 and 3 · CPC title

• C08G73/101

  containing chain terminating or branching agents · CPC title

• C07F9/65517 Primary

  condensed with carbocyclic rings or carbocyclic ring systems · CPC title

• C08G73/10

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title