Triazine-based membranes for gas separation

Patent metadata

Field	Value
Publication number	US-12297322-B2
Application number	US-202117517993-A
Country	US
Kind code	B2
Filing date	Nov 3, 2021
Priority date	Nov 9, 2020
Publication date	May 13, 2025
Grant date	May 13, 2025

Abstract

A polymer composition comprising a covalent triazine framework having the following structure:

wherein: each asterisk (*) in A units denotes a point of covalent bonding with an asterisk in B units, and each asterisk (*) in B units denotes a point of covalent bonding with an asterisk in A units; r is an integer of 1-3; R is a fluorinated hydrocarbon containing at least two aromatic rings and at least one ether linkage between aromatic rings; the composition includes a multiplicity of A units and multiplicity of B units; and a portion of the connection points are terminated by endcapping nitrile groups. Also described are methods for producing the polymer and a microporous carbon material produced by pyrolysis of the porous polymer membrane. Also described are methods for using the polymer and microporous carbon material for gas or liquid separation, filtration, or purification.

First claim

What is claimed is:

1. A polymer composition comprising a covalent triazine framework having the following structure:

wherein:
each asterisk (*) in A units denotes a point of covalent bonding with an asterisk in B units, and each asterisk (*) in B units denotes a point of covalent bonding with an asterisk in A units;
r is an integer of 1-3;
R is a fluorinated hydrocarbon containing at least two aromatic rings and at least one ether linkage between aromatic rings;
the composition includes a multiplicity of A units and multiplicity of B units; and
a portion of connection points are terminated by endcapping nitrile groups.

2. The polymer composition of claim 1 , wherein at least a portion of the aromatic rings in R are substituted with at least one fluorine atom per aromatic ring.

3. The polymer composition of claim 1 , wherein R contains at least one fluorinated alkyl or alkenyl group.

4. The polymer composition of claim 1 , wherein R has the following structure:

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are independently selected from hydrogen atom, fluorine atom, hydrocarbon groups (R′) containing 1-12 carbon atoms, —OR″ groups, —SR″ groups, and —NR″2 groups, wherein R″ is independently selected from hydrogen atom and R′ groups;
wherein the R′ hydrocarbon group is optionally substituted with one or more fluorine atoms to result in a fluorinated hydrocarbon group; and
wherein any two adjacent groups selected from R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 groups are optionally interconnected.

5. The polymer composition of claim 4 , wherein one or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are hydrogen atoms and one or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are fluorine atoms.

6. The polymer composition of claim 4 , wherein one or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are hydrogen atoms and one or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are fluorinated alkyl groups.

7. The polymer composition of claim 6 , wherein none of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 are fluorine atoms.

8. The polymer composition of claim 1 , wherein R has the following structure:

wherein R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 are independently selected from hydrogen atom, fluorine atom, hydrocarbon groups (R′) containing 1-12 carbon atoms, —OR″ groups, —SR″ groups, and —NR″2 groups, wherein R″ is independently selected from hydrogen atom and R′ groups;
wherein the R′ hydrocarbon group is optionally substituted with one or more fluorine atoms to result in a fluorinated hydrocarbon group; and
wherein any two adjacent groups selected from R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 groups are optionally interconnected.

9. The polymer composition of claim 8 , wherein one or more of R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 are hydrogen atoms and one or more of R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 are fluorine atoms.

10. The polymer composition of claim 8 , wherein one or more of R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 are hydrogen atoms and one or more of R 17 , R 18 R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 are fluorinated alkyl groups.

11. The polymer composition of claim 10 , wherein none of R 17 , R 18 , R 19 , R 20 , R 21 R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 are fluorine atoms.

12. The polymer composition of claim 1 , wherein the composition possesses micropores having a size of 0.1 nm to 2 nm.

13. The polymer composition of claim 1 , wherein the composition possesses ultramicropores having a size of 0.1 nm to 1 nm.

14. The polymer composition of claim 1 , wherein the composition is microporous and in the shape of a membrane having a thickness of up to 200 microns.

15. A method for at least partially separating carbon dioxide gas from a carbon dioxide-containing mixture of gases, the method comprising passing the carbon dioxide-containing mixture of gases through a microporous polymer membrane, wherein gas exiting the microporous polymer membrane has an increased carbon dioxide concentration relative to the initial carbon dioxide-containing mixture of gases not passed through the microporous polymer membrane;
wherein said microporous polymer membrane possesses micropores having a size of 0.1 nm to 2 nm and has a covalent triazine framework composition having the following structure:

wherein:
each asterisk (*) in A units denotes a point of covalent bonding with an asterisk in B units, and each asterisk (*) in B units denotes a point of covalent bonding with an asterisk in A units;
r is an integer of 1-3;
R is a fluorinated hydrocarbon containing at least two aromatic rings and at least one ether linkage between aromatic rings;
the composition includes a multiplicity of A units and multiplicity of B units; and
a portion of connection points are terminated by endcapping nitrile groups.

16. The method of claim 15 , wherein the microporous polymer membrane possesses ultramicropores having a size of 0.1 nm to 1 nm.

17. The method of claim 15 , wherein the microporous polymer membrane has a thickness of up to 200 microns.

18. The method of claim 15 , wherein the carbon dioxide-containing mixture of gases is flue gas containing at least 5% carbon dioxide.

Assignees

• Ut Battelle Llc
• Univ Tennessee Res Found

Inventors

• Yang Zhenzhen
• Popovs Ilja
• Dai Sheng

Classifications

• B01D2325/02834

  more than 0.1 and up to 1 µm · CPC title

• B01D61/027

  Nanofiltration · CPC title

• B01D2325/04

  Characteristic thickness · CPC title

• B01D71/62

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain · CPC title

• B01D69/02

  characterised by their properties · CPC title