Perfluoropyridine based polymers obtained via radical initiated methods

Patent metadata

Field	Value
Publication number	US-2024309128-A1
Application number	US-202418598136-A
Country	US
Kind code	A1
Filing date	Mar 7, 2024
Priority date	Mar 13, 2023
Publication date	Sep 19, 2024
Grant date	—

Abstract

The synthesis of the fluorinated monomer, 2-((perfluoropyridin-4-yl)amino)ethyl methacrylate, and the use of the same in the preparation of fluorinated homo- and copolymers is provided. Such monomer was designed to contain a terminal methacrylate group, allowing for polymerization through free-radical techniques, both chain-growth and reversible addition-fragmentation chain-transfer methods. The monomer was designed to be compatible with other commercially available monomers and solvents to facilitate ease of copolymerization through free-radical polymerization techniques. The polymerization does not require perfluorinated alkyl substances or perfluorooctanoic acids or related compounds in the synthesis of the fluoropolymers.

First claim

What is claimed is:

1 . A monomer having the following formula:

wherein
R 1 is H or a hydrocarbon;
X is O, NH, or S;
Y is a hydrocarbon; and
Z is O, NH, or S.

2 . The monomer of claim 1 wherein:
R 1 is H, methyl, ethyl, propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl,
n-pentyl, n-hexyl, n-hepyl, n-octyl, or phenyl; and
Y is ethyl, propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl,
n-pentyl, n-hexyl, n-hepyl, n-octyl, or phenyl.

3 . The monomer of claim 2 wherein: R 1 is H or methyl, Y is ethyl or phenyl, X is O.

4 . A polymer comprising the monomer of claim 1 .

5 . The polymer of claim 4 , said polymer having Structure 1 or Structure 2 below:

a) wherein for Structure 1
R 1 is H or a hydrocarbon;
X=O, NH, or S;
Y=a hydrocarbon;
Z=O, NH, or S; and
the indice n is an integer from 20 to 150; and

b) wherein for Structure 2
R 1 , R 2 , or R 3 are each independently H or a hydrocarbon;
X=O, NH, or S;
Y=a hydrocarbon;
Z=O, NH, or S; and
the indice n is an integer from 20 to 150.

6 . The polymer of claim 5 wherein
a) for Structure 1 R 1 is H, methyl, ethyl, propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, n-hexyl, n-hepyl, n-octyl, or phenyl; and
Y is ethyl, propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, n-hexyl, n-hepyl, n-octyl, or phenyl; and

b) for Structure 2:
R 1 is H, methyl, ethyl, propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, n-hexyl, n-hepyl, n-octyl, or phenyl;
R 2 and are R 3 are each independently H, methyl, ethyl, propyl, iso-propyl, n-butyl, tertbutyl, sec-butyl, n-pentyl, n-hexyl, n-hepyl, n-octyl, phenyl, O(C═O)CH 3 , O(C═O)OH, Cl, F, CN; and
Y is ethyl, propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, n-hexyl, n-hepyl, n-octyl, or phenyl.

7 . The polymer of claim 6 wherein
a) for Structure 1 R 1 is H or methyl, Y is ethyl or phenyl, and X is O; and
b) for Structure 2 R 1 is H or methyl, R 2 is H or methyl, R 3 is O(C═O)CH 3 , Y is ethyl or phenyl, and X is O.

8 . The polymer of claim 4 , said polymer having a number average molecular weight of from about 5,000 Da to about 50,000 Da.

9 . The polymer of claim 4 , said polymer having a number average molecular weight of from about 8,000 Da to about 75,000 Da.

10 . The polymer of claim 4 , said polymer having a polydispersity of from about 1.2 to about 4.8.

11 . An article comprising the polymer of claim 4 .

12 . The article of claim 11 , said article being a textile, or a membrane.

13 . A process of making a monomer comprising reacting a monomeric precursor having Structure 1 and an acrylol chloride having Structure 2 in the presence of an amine base, preferably said amine base is triethylamine

a) wherein for Structure 1
X=O, NH, or S;
Y=a hydrocarbon; and
Z=O, NH, or S; and

b) for Structure 2 R 1 is H or a hydrocarbon.

14 . The process of claim 13 wherein:
a) for Structure 1 Y is ethyl, propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, n-hexyl, n-hepyl, n-octyl, or phenyl; and
b) for Structure 2 R 1 is H, methyl, ethyl, propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, n-hexyl, n-hepyl, n-octyl, or phenyl.

15 . The process of claim 13 wherein for Structure 1 Y is ethyl or phenyl, X is O; and for Structure 2 R 1 is H or methyl.

16 . A process of making a polymer comprising polymerizing a monomer having Structure 3 below:

wherein
R 1 is H or a hydrocarbon;
X=O, NH, or S;
Y=a hydrocarbon; and
Z=O, NH, or S.

17 . The process of claim 16 wherein for said monomer having Structure 3:
R 1 is H, methyl, ethyl, propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, n-hexyl, n-hepyl, n-octyl, or phenyl; and
Y=ethyl, propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, n-pentyl, n-hexyl, n-hepyl, n-octyl, or phenyl.

18 . The process of claim 16 wherein for said monomer having Structure 3 R 1 is H or methyl, Y is ethyl or phenyl, X is O.

Assignees

• Us Gov Air Force

Inventors

• Jennings Abby R
• Iacono Scott T
• Auleciems Zachary J
• Lochmaier Emeline C

Classifications

• C08F26/06 Primary

  by a heterocyclic ring containing nitrogen · CPC title

• C07D213/74 Primary

  Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals · CPC title

• C08F2438/02

  Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO] · CPC title