Mechanochemical based synthesis of perfluoropyridine monomers for polymerization

Patent metadata

Field	Value
Publication number	US-11970449-B2
Application number	US-202318202352-A
Country	US
Kind code	B2
Filing date	May 26, 2023
Priority date	Oct 4, 2021
Publication date	Apr 30, 2024
Grant date	Apr 30, 2024

Abstract

The present invention relates to a mechanochemical based synthesis of perfluoropyridine monomers, polymers made using such monomers and methods of making and using articles comprising such polymers. Such perfluoropyridine monomers are easily chemically tuned have the strength needed for high temperature applications and the flexibility needed for low temperature applications. In addition, to the aforementioned monomers, a mechanochemical based synthesis for such perfluoropyridine monomers is provided. All of the aforementioned performance application advantages are also found in polymers comprising Applicants' perfluoropyridine monomers.

First claim

What is claimed is:

1. A process of making a monomer having the following formula:

wherein
a) R 1 is a branched unsubstituted hydrocarbon, unbranched unsubstituted hydrocarbon, branched substituted hydrocarbon or unbranched substituted hydrocarbon; and
b) each R 2 is independently fluorine, a branched unsubstituted hydrocarbon, unbranched unsubstituted hydrocarbon, branched substituted hydrocarbon or unbranched substituted hydrocarbon;
said process comprising combining a nucleophile, a carbonate and a fluoro-substituted aromatic in a mill to form a combined composition or combining a nucleophile, a carbonate and a fluoro-substituted aromatic to form a combined composition; and milling said combined composition.

2. The process according to claim 1 , wherein:
a) said nucleophile is selected from the group consisting of a tetrel, a pnictogen, a chalcogen and mixtures thereof;
b) said carbonate is selected from the group consisting of potassium carbonate and cesium carbonate; and
c) said fluoro-substituted aromatic material is selected from the group consisting of a fluoro-substituted aromatic molecule, a polymer comprising a fluoro-substituted aromatic moiety and mixtures thereof.

3. The process according to claim 1 , wherein said milling is conducted using a ball mill, a planetary ball mill, vibration ball mill, a stirring ball mill, a pin ball mill, a rolling ball mill, or an auger mill.

4. A process of making a polymer network said process comprising combining a nucleophile and a monomer having the following formula:

wherein
a) R 1 is a branched unsubstituted hydrocarbon, unbranched unsubstituted hydrocarbon, branched substituted hydrocarbon or unbranched substituted hydrocarbon; and
b) each R 2 is independently fluorine, a branched unsubstituted hydrocarbon, unbranched unsubstituted hydrocarbon, branched substituted hydrocarbon or unbranched substituted hydrocarbon;
in a mill to form a combined composition or combining a nucleophile and said monomer to form a combined composition and then placing said combined composition in a mill; and milling the said combined composition.

5. The process of claim 4 wherein nucleophile is selected from the group consisting of nucleophile is selected from the group consisting of a tetrel, a pnictogen, a chalcogen and mixtures thereof.

6. The process of claim 4 wherein a second monomer, other than a monomer having the following formula:

wherein
a) R 1 is a branched unsubstituted hydrocarbon, unbranched unsubstituted hydrocarbon, branched substituted hydrocarbon or unbranched substituted hydrocarbon; and
b) each R 2 is independently fluorine, a branched unsubstituted hydrocarbon, unbranched unsubstituted hydrocarbon, branched substituted hydrocarbon or unbranched substituted hydrocarbon;
is added to said ball mill during said process.

7. The process of claim 6 wherein, said second monomer is added after said combined composition is formed.

Assignees

• Us Gov Air Force
• Us Air Force

Inventors

• Iacono Scott T
• Friesen Chadron M

Classifications

• C07D213/61 Primary

  Halogen atoms or nitro radicals · CPC title

• C08G73/0627

  with only one nitrogen atom in the ring · CPC title

• C10G71/00 Primary

  Treatment by methods not otherwise provided for of hydrocarbon oils or fatty oils for lubricating purposes · CPC title

• C10M147/04

  Monomer containing carbon, hydrogen, halogen and oxygen · CPC title

• C10M169/041

  the additives being macromolecular compounds only · CPC title