IP Library › Granted Patent US 12,297,322
Granted Patent B2
US 12,297,322 · App. 17/517,993 · Granted May 13, 2025

Triazine-based membranes for gas separation

Inventors: Zhenzhen Yang (Knoxville, TN); Ilja Popovs (Knoxville, TN); Sheng Dai (Knoxville, TN)
Assignees: UT-Battelle, LLC; University of Tennessee Research Foundation
C08G73/0644B01D53/228B01D61/027B01D69/02B01D71/62C08G73/065B01D2325/02834B01D2325/04
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Quick Facts
Patent No.
US 12,297,322
App. No.
17/517,993
Granted
May 13, 2025
Kind
B2
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.

Claims (37)

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.

Assignments (3)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 6, 2022
From: POPOVS, ILJA; DAI, SHENG
To: UT-BATTELLE, LLC
Reel/Frame 059518/0253 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 6, 2022
From: YANG, ZHENZHEN
To: UNIVERSITY OF TENNESSEE RESEARCH FOUNDATION
Reel/Frame 059518/0323 →
CONFIRMATORY LICENSE Recorded Feb 22, 2022
From: UT-BATTELLE, LLC
To: U. S. DEPARTMENT OF ENERGY
Reel/Frame 059066/0004 →
Continuity (2)
Provisional Application 63111149 · Nov 9, 2020
Related Publication 20220145008A1 · May 12, 2022
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