Synthesis and polymerization of oligomeric aliphatic-aromatic based phthalonitriles

Patent metadata

Field	Value
Publication number	US-9394404-B2
Application number	US-201514968099-A
Country	US
Kind code	B2
Filing date	Dec 14, 2015
Priority date	Dec 16, 2014
Publication date	Jul 19, 2016
Grant date	Jul 19, 2016

Abstract

A phthalonitrile compound having the formula below. The value n is a positive integer. Each R has a hydrocarbon chain optionally having —O— or —SiR′ 2 —O—. Each R′ is an aliphatic group. Each Ar is an aromatic group with the proviso that Ar contains at least two aromatic rings when n is 1 and R is an alkylene group. A method of: reacting an excess of a dihydroxyaromatic compound with a dihalocompound to form an oligomer; and reacting the oligomer with 4-nitrophthalonitrile to form the phthalonitrile compound, where Ar is an aromatic group.

First claim

What is claimed is:

1. A phthalonitrile compound having the formula:

wherein n is a positive integer;
wherein each R comprises a hydrocarbon chain optionally comprising —O— or —SiR′ 2 —O—;
wherein each R′ is an aliphatic group; and
wherein each Ar is an aromatic group with the proviso that Ar comprises at least two aromatic rings when n is 1 and R is an alkylene group.

2. The phthalonitrile compound of claim 1 , wherein each Ar is —C 6 H 4 —C(CH 3 ) 2 —C 6 H 4 —, —C 6 H 4 —C(CF 3 ) 2 —C 6 H 4 —, or —C 6 H 4 —SO 2 —C 6 H 4 —.

3. The phthalonitrile compound of claim 1 , wherein each Ar is m-phenylene.

4. The phthalonitrile compound of claim 1 , wherein each R is an alkylene group or hexylene.

5. The phthalonitrile compound of claim 1 , wherein each R is —C 2 H 4 —O—C 2 H 4 —.

6. The phthalonitrile compound of claim 1 , wherein each R is
—CH 3 —Si(CH 3 ) 2 —O—Si(CH 3 ) 2 —CH 3 —.

7. The phthalonitrile compound of claim 1 , wherein the phthalonitrile compound is:

8. The phthalonitrile compound of claim 1 , wherein the phthalonitrile compound is:

9. The phthalonitrile compound of claim 1 , wherein the phthalonitrile compound is:

10. The phthalonitrile compound of claim 1 , wherein the phthalonitrile compound is:

11. The phthalonitrile compound of claim 1 , wherein the phthalonitrile compound is:

12. A method comprising:
curing the phthalonitrile compound of claim 1 with a curing additive to form a thermoset.

13. The method of claim 12 , wherein the curing additive is bis(3-[4-aminophenoxy]phenyl)sulfone, bis[4-(4-aminophenoxy) phenyl]sulfone, 1,4-bis(3-aminophenoxy)benzene, or 1,3-bis(3-aminophenoxy)benzene.

14. A method comprising:
reacting an excess of a dihydroxyaromatic compound having the formula HO—Ar—OH with a dihalocompound having the formula X—R—X to form an oligomer having the formula

wherein each X is a halide;
wherein each R comprises a hydrocarbon chain optionally comprising —O— or —SiR′ 2 —O—;
wherein each R′ is an aliphatic group; and
wherein each Ar is an aromatic group; and

reacting the oligomer with 4-nitrophthalonitrile to form a phthalonitrile compound having the formula:

15. The method of claim 14 , wherein the phthalonitrile compound is:

16. The method of claim 14 , wherein the phthalonitrile compound is:

17. The method of claim 14 , wherein the phthalonitrile compound is:

18. The method of claim 14 , wherein the phthalonitrile compound is:

19. The method of claim 14 , wherein the phthalonitrile compound is:

20. The method of claim 14 , further comprising:
curing the phthalonitrile compound with a curing additive to form a thermoset.

Assignees

• Us Navy

Inventors

• Laskoski Matthew
• Keller Teddy M
• Saab Andrew P

Classifications

• C07C255/54

  containing cyano groups and etherified hydroxy groups bound to the carbon skeleton · CPC title

• C07F7/0889

  Reactions not involving the Si atom of the Si-O-Si sequence · CPC title

• C07F7/0854

  Chemistry & Metallurgy · mapped topic

• C08G65/4006 Primary

  (I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X) · CPC title

• C07C253/30

  by reactions not involving the formation of cyano groups · CPC title