Phthalonitriles derived from polyphenols

Patent metadata

Field	Value
Publication number	US-9920165-B2
Application number	US-201615084760-A
Country	US
Kind code	B2
Filing date	Mar 30, 2016
Priority date	Apr 23, 2015
Publication date	Mar 20, 2018
Grant date	Mar 20, 2018

Abstract

A method of making an organic salt comprising: reacting a polyphenol with a base and optionally a dihaloaromatic compound. The polyphenol is resveratrol; dihydroresveratrol; 4,4′-(but-2-ene-1,4-diyl)bis-2-methoxyphenol; 4,4′-(1,4-butane-diyl)bis-2-methoxyphenol; 1-ethyl-2-methyl-3-(4-hydroxyphenyl)-5-hydroxyindane; 4,4′-(ethane-1,1-diyl)diphenol; 5,5′-methylenebis(2-methoxy-4-methylphenol); 4,4′-methylenebis(5-isopropyl-2-methylphenol); 4,4′-(1-ethyl-2-methyl-1,3-propanediyl)bisphenol; or 5,5′-(ethane-1,1-diyl)bis(2-methoxy-4-methylphenol. The dihaloaromatic compound if present comprises a carbonyl group, a sulfonyl group, a sulfinyl group, or a phosphoryl group. There is a molar excess of the hydroxy groups of the polyphenol relative to halo groups of the dihaloaromatic compound if present. The corresponding phthalonitrile monomers and thermosets made from the organic salts are disclosed.

First claim

What is claimed is:

1. A method of making an organic salt comprising:
reacting a polyphenol with a base and optionally a dihaloaromatic compound;
wherein the polyphenol is resveratrol; dihydroresveratrol;
4,4′-(but-2-ene-1,4-diyl)bis-2-methoxyphenol;
4,4′-(1,4-butane-diyl)bis-2-methoxyphenol;
1-ethyl-2-methyl-3-(4-hydroxyphenyl)-5-hydroxyindane;
4,4′-(ethane-1,1-diyl)diphenol;
5,5′-methylenebis(2-methoxy-4-methylphenol);
4,4′-methylenebis(5-isopropyl-2-methylphenol);
4,4′-(1-ethyl-2-methyl-1,3-propanediyl)bisphenol; or
5,5′-(ethane-1,1-diyl)bis(2-methoxy-4-methylphenol);

wherein the dihaloaromatic compound if present comprises a carbonyl group, a sulfonyl group, a sulfinyl group, or a phosphoryl group; and
wherein there is a molar excess of the hydroxy groups of the polyphenol relative to halo groups of the dihaloaromatic compound if present.

2. The organic salt made by the method of claim 1 .

3. The organic salt of claim 2 , wherein the base is potassium carbonate or a combination of potassium carbonate and sodium hydroxide.

4. A method comprising:
reacting the organic salt of claim 2 with 4-nitrophthalonitrile to form a phthalonitrile monomer.

5. A phthalonitrile monomer made by a method comprising;
reacting a polyphenol with a base and optionally a dihaloaromatic compound to form an organic salt;
wherein the polyphenol is resveratrol; dihydroresveratrol;
4,4′-(but-2-ene-1,4-diyl)bis-2-methoxyphenol;
4,4′-(1,4-butane-diyl)bis-2-methoxyphenol;
1-ethyl-2-methyl-3-(4-hydroxyphenyl)-5-hydroxyindane;
4,4′-(ethane-1,1-diyl)diphenol;
5,5′-methylenebis(2-methoxy-4-methylphenol);
4,4′-methylenebis(5-isopropyl-2-methylphenol);
4,4′-(1-ethyl-2-methyl-1,3-propanediyl)bisphenol; or
5,5′-(ethane-1,1-diyl)bis(2-methoxy-4-methylphenol);

wherein the dihaloaromatic compound if present comprises a carbonyl group, a sulfonyl group, a sulfinyl group, or a phosphoryl group; and
wherein there is a molar excess of the hydroxy groups of the polyphenol relative to halo groups of the dihaloaromatic compound if present; and

reacting the organic salt with 4-nitrophthalonitrile to form the phthalonitrile monomer.

6. The phthalonitrile monomer of claim 5 , wherein the organic salt has the formula:

wherein each M is independently K or Na.

7. The phthalonitrile monomer of claim 5 , wherein the organic salt has the formula:

wherein each M is independently K or Na.

8. The phthalonitrile monomer of claim 5 , wherein the organic salt has the formula:

wherein each M is independently K or Na.

9. The phthalonitrile monomer of claim 5 , wherein the dihaloaromatic compound is a dihalobenzophenone, 4,4′-dichlorobenzophenone, a dihalophenylsulfone, bis-4-(chlorophenyl)sulfone, a dihalophenylsulfoxide, or a dihalophenyl phosphine oxide.

10. The phthalonitrile monomer of claim 5 , wherein the organic salt has the formula:

wherein n is a positive integer; and
wherein each M is independently K or Na.

11. The phthalonitrile monomer of claim 5 , wherein the organic salt has the formula:

wherein n is a positive integer; and
wherein each M is independently K or Na.

12. The phthalonitrile monomer of claim 5 , wherein the organic salt has the formula:

wherein n is a positive integer; and
wherein each M is independently K or Na.

13. The phthalonitrile monomer of claim 5 , wherein the organic salt has the formula:

wherein n is a positive integer; and
wherein each M is independently K or Na.

14. The phthalonitrile monomer of claim 5 , wherein the organic salt has the formula:

wherein n is a positive integer; and
wherein each M is independently K or Na.

15. The phthalonitrile monomer of claim 5 , wherein the organic salt has the formula:

wherein n is a positive integer; and
wherein each M is independently K or Na.

16. The phthalonitrile monomer of claim 5 , wherein the organic salt has the formula:

wherein n is a positive integer; and
wherein each M is independently K or Na.

17. The phthalonitrile monomer of claim 5 , wherein the organic salt further comprises a salt of the polyphenol.

18. A method comprising:
curing the phthalonitrile monomer of claim 5 to form a thermoset.

19. The thermoset made by the method of claim 18 .

20. A method comprising:
providing a first phthalonitrile monomer made by a method comprising:
reacting a first polyphenol with a first base and optionally a first dihaloaromatic compound to form a first organic salt;
wherein there is a molar excess of the hydroxy groups of the first polyphenol relative to halo groups of the first dihaloaromatic compound if present; and

reacting the first organic salt with 4-nitrophthalonitrile to form the first phthalonitrile monomer;

optionally, providing a second phthalonitrile monomer made by a method comprising:
reacting a second polyphenol with a second base and optionally a second dihaloaromatic compound to form a second organic salt;
wherein there is a molar excess of the hydroxy groups of the second polyphenol relative to halo groups of the second dihaloaromatic compound if present; and

reacting the second organic salt with 4-nitrophthalonitrile to form the second phthalonitrile monomer;
wherein the first polyphenol and the second polyphenol if present are independently selected from resveratrol; dihydroresveratrol;
4,4′-(but-2-ene-1,4-diyl)bis-2-methoxyphenol;
4,4′-(1,4-butane-diyl)bis-2-methoxyphenol;
1-ethyl-2-methyl-3-(4-hydroxyphenyl)-5-hydroxyindane;
4,4′-(ethane-1,1-diyl)diphenol;
5,5′-methylenebis(2-methoxy-4-methylphenol);
4,4′-methylenebis(5-isopropyl-2-methylphenol);
4,4′-(1-ethyl-2-methyl-1,3-propanediyl)bisphenol; or
5,5′-(ethane-1,1-diyl)bis(2-methoxy-4-methylphenol);

wherein the first dihaloaromatic compound if present and the second dihaloaromatic compound if present each comprise a group independently selected from a carbonyl group, a sulfonyl group, a sulfinyl group, or a phosphoryl group;
wherein the first base and the second base if present are the same or different;
wherein the first phthalonitrile monomer and the second phthalonitrile monomer if present are different; and

making a phthalonitrile mixture by mixing the first phthalonitrile monomer with one or more of: the second phthalonitrile monomer if present; a monophthalonitrile compound; 1,3,5-tris(3,4-dicyanophenoxy)benzene;

Assignees

• Us Gov Sec Navy
• Us Navy

Inventors

• Laskoski Matthew
• Keller Teddy M

Classifications

• C08G65/48

  Polymers modified by chemical after-treatment · CPC title

• C07C49/84

  containing ether groups, [IMAGE cpc-sch-C07C-0958.gif] groups,[IMAGE cpc-sch-C07C-0959.gif] groups, or[IMAGE cpc-sch-C07C-0960.gif] groups · CPC title

• C07C45/64

  by introduction of functional groups containing oxygen only in singly bound form · CPC title

• C07C39/17

  containing other rings in addition to the six-membered aromatic rings {, e.g. cyclohexylphenol} · CPC title

• C07C39/16

  Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes · CPC title