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CN-122029208-A - Functionalized polymers and uses

CN122029208ACN 122029208 ACN122029208 ACN 122029208ACN-122029208-A

Abstract

The present application relates to polymers (such as polymers of intrinsic microporosity). Comprising a polymeric backbone comprising a twisted aromatic moiety and at least one pendent group as defined herein.

Inventors

  • SONG QILEI
  • WANG ANQI
  • Yang Dingchang
  • Meng Naiqi
  • T.P.W.Y.Huang
  • S. Iguodala

Assignees

  • 帝国理工创新有限公司

Dates

Publication Date
20260512
Application Date
20240911
Priority Date
20230911

Claims (20)

  1. 1. A polymer (such as an inherently microporosity polymer) comprising: a polymeric backbone comprising a twisted aromatic moiety, and At least one of the pendant groups comprises: ; ; ; , Or (b) Wherein R is an aliphatic or aromatic carboxylic acid group; wherein p is 1 to 100; Wherein G 1 is C (NH 2 ) =noh, C (=o) OH or S (=o) 2 OH; wherein G 2 is S (=o) 2 OH; ; Or (b) 。
  2. 2. The polymer of claim 1, wherein the polymer is a copolymer of the formula: (IV) Or (b) (V) Wherein each of CA 1 and CA 2 is independently a twisted aromatic moiety (which may be the same or different), or a linear aromatic moiety (which may be the same or different), Wherein S 1a is the pendant group, wherein the pendant group may be bonded via one bond or two bonds; Wherein each of R 1a 、R 2a and R 3a is independently hydrogen, or optionally substituted alkyl, haloalkyl, optionally substituted aryl or haloaryl (e.g., optionally wherein the aryl is bicyclic), optionally wherein each R 3a is independently perfluorophenyl or 2, 4-bistrifluoromethylphenyl, or wherein R 1a is absent, Wherein m is 0 to 1000 (preferably 100 to 500), and Wherein n is 0 to 1000 (preferably 100 to 500); wherein at least one of m and n is 1, and wherein the sum of m and n is at least 10, optionally at least 200, optionally at least 500, such as at least 800, optionally at least 1000; Wherein R 1a is absent when the group is attached to the polymeric backbone via two bonds (optionally forming a ring).
  3. 3. The polymer of claim 1, wherein the polymer is a copolymer of the formula: (VI) Wherein a 1 is an aromatic group comprising at least one phenyl group, such as two or three phenyl groups; Wherein CA 1 is a twisted aromatic moiety; Wherein each of S 1a and S 2a is independently the pendant group (which may be the same or different), wherein the pendant groups may be bonded by one bond or two bonds; Wherein R 1a and R 2a are each independently absent, hydrogen, or optionally substituted alkyl, haloalkyl, optionally substituted aryl or haloaryl (e.g., optionally wherein the aryl is bicyclic); Wherein m is 1 to 1000 (preferably 100 to 500); Wherein n is 1 to 1000 (preferably 100 to 500); Wherein the sum of m and n is at least 10, optionally at least 200, optionally at least 500, such as at least 800, optionally at least 1000; Wherein R 1a is absent when the pendant group is bonded to an adjacent twisted aromatic moiety twice (optionally forming a ring).
  4. 4. A polymer according to any preceding claim, wherein: (a) Each of the twisted aromatic moieties comprises one of the following, optionally substituted: Wherein the point of attachment can be any suitable substitution of H on the aromatic ring system, and is optionally shown as a black dot; wherein each R 0 is independently selected from H, OH, C 1-3 alkyl (preferably CH 3 ), or C 1-3 alkoxy (preferably OCH 3 ); (b) Each of the twisted aromatic moieties comprises one of the following, optionally substituted: Wherein each of R 5 to R 24 、R 25 、R 26 、R 28 and R 29 is independently selected from ; Wherein n is 1 to 20; And wherein the point of attachment may be any suitable substitution of a hydrogen on the aromatic ring system.
  5. 5. The polymer of any one of claims 75 to 93, wherein the polymeric backbone further comprises aromatic groups, optionally wherein the polymeric backbone further comprises one or more of the following: wherein the point of attachment may be any suitable substitution of hydrogen on the aromatic ring system.
  6. 6. A polymer according to any preceding claim, wherein: (a) The twisted aromatic moieties are linked by a linker moiety to form the backbone, and/or (B) The backbone is configured to prevent free rotation of each twisted aromatic moiety relative to the backbone, Optionally, wherein the linker moiety is configured to prevent free rotation of each torsional aromatic moiety relative to the backbone (e.g., wherein the linker moiety is bonded to at least two positions on each torsional aromatic moiety).
  7. 7. The polymer of claim 4, wherein the linker moiety comprises an optionally substituted phenyl group or heteroaryl group, optionally wherein the linker moiety is optionally substituted: Or (b) Or (b) Optionally, wherein the linker moiety is Or (b) Or (b) ; Wherein each S 1 is independently the pendant group, Optionally wherein S 1 is Wherein p is 1 to 100 Or wherein the linker moiety is a single bond or Or C 1-3 alkyl, or C 1-3 alkoxy, preferably wherein the linker moiety is a single bond.
  8. 8. The polymer of any one of claims 1 to 5, wherein the polymer is of the formula: (EP1) (EP2) (EP3) Wherein m is 1 to 1000 (preferably 100 to 500); Wherein x is 1 to 1000 (preferably 100 to 500); Wherein y is 1 to 1000 (preferably 100 to 500); Wherein p is 1 to 100.
  9. 9. The polymer of any preceding claim, wherein the polymer is of the formula: (EFP1) (EFP2) (EFP3) (EFP4) (EFP5) Wherein n is 1 to 1000 (preferably 100 to 500); Wherein m is 1 to 1000 (preferably 100 to 500); Wherein x is from 1 to 1000 (preferably from 100 to 500), and Wherein y is 1 to 1000 (preferably 100 to 500).
  10. 10. The polymer of any preceding claim, wherein the polymer is of the formula: (AP1) (AP2) (AP5) Wherein n is 1 to 1000 (preferably 100 to 500); Wherein m is 1 to 1000 (preferably 100 to 500); Wherein x is 1 to 1000 (preferably 100 to 500); wherein y is 1 to 1000 (preferably 100 to 500).
  11. 11. The polymer of any preceding claim, wherein the polymer is of the formula: (ZP1) (ZP3) Wherein x is 1 to 1000 (preferably 100 to 500); wherein y is 1 to 1000 (preferably 100 to 500).
  12. 12. A polymer (such as an inherently microporosity polymer) comprising: a polymeric backbone comprising a twisted aromatic moiety, and At least one of the pendant groups comprises: ; Wherein the or each side group is attached to the polymeric backbone; And wherein the polymeric backbone further comprises As moieties suspended thereby (optionally wherein the moieties are between adjacent twisted aromatic moieties), wherein R 1 -R 5 is optionally substituted with hydrogen, fluorine, and CF 3 .
  13. 13. An ion exchange membrane comprising the polymer of any one of claims 1 to 10.
  14. 14. Use of an ion exchange membrane according to claim 11 in the following: (a) Electrodialysis, or (B) Redox flow battery, or (C) Ion separation, such as separating Li + from Mg 2+ , for example in an aqueous solution thereof.
  15. 15. An electrodialysis ion exchange membrane comprising a polymer (such as an inherently microporous polymer) comprising: a polymeric backbone comprising a twisted aromatic moiety, and At least one pendant group comprising C (=noh) NH 2 or COOH.
  16. 16. Use of a polymer of the formula: Or (b) 。
  17. 17. A method of preparing a polymer (such as an inherently microporosity polymer), suitably a polymer according to any one of claims 1 to 10, the method comprising polymerizing: A monomer a comprising a twisted aromatic moiety CA 1 ; A monomer B comprising a pendent group S 1a or a pendent group precursor S p ; the method is for providing a polymer comprising a polymeric backbone comprising a twisted aromatic moiety and the at least one pendant group or pendant group precursor; Optionally, wherein the method comprises polymerizing the monomer B comprising a pendant group precursor S p , and wherein the method further comprises modifying the pendant group precursor S p of the polymeric backbone to form a pendant group S 1a .
  18. 18. The method of claim 17, wherein monomer B comprises a pendent precursor S p selected from one of: Or (b) Or (b) ; Wherein each R 1 -R 5 is independently selected from hydrogen, fluorine, and CF 3 ; Such as: 。
  19. 19. The method of claim 17 or 18, wherein the pendant group or pendant group precursor comprises the following moieties: And wherein modifying the pendant group precursor forms a pendant group selected from the group consisting of: 。
  20. 20. The method of claim 17 or 18, wherein the pendant precursor comprises the following moieties: And wherein modifying the pendant group precursor forms a pendant group selected from the group consisting of: 。

Description

Functionalized polymers and uses Technical Field The present disclosure relates to Polymers of Intrinsic Microporosity (PIM). More particularly, but not necessarily exclusively, the present disclosure relates to ion-conductive ionomer binders useful in ion-exchange membranes, in separation membranes for molecular and ion separation, or in membrane electrode assemblies in electrochemical devices. Background Ion conductive polymer membranes are components in a wide range of separation processes such as electrodialysis and diffusion dialysis, and in electrochemical devices for energy conversion and storage, including fuel cells, electrolytic cells, and redox flow batteries. In these devices, the membrane is a semi-permeable membrane separating the anode and cathode compartments from each other while allowing selective transport of small ions for charge balance during operation. Similarly, the ionomer acts as a catalyst binder in the membrane electrode assembly, which stabilizes the catalyst while facilitating ion transport. It is desirable to impart both high ionic conductivity and high charge and size-based selectivity of membranes and ionomers to promote efficiency, energy/power density, and life time of these low carbon technologies toward significantly reduced cost improvements, which is desirable for wider deployment. However, all existing membranes suffer from a compromise between conductivity and ion transport selectivity. Currently, all commercial ion conducting membranes are based on ion exchange polymers that contain ionic groups, such as perfluorosulfonic acid polymers, chemically bonded to their hydrophobic polymer backbone or side chains. However, despite its fast ionic conduction, the selectivity for ions of different sizes and charges is still unsatisfactory. In addition, the reference membrane material Nafion ™ is expensive. It is desirable to provide improved films and/or to eliminate and/or alleviate one or more of the disadvantages of known films, whether or not such disadvantages are identified herein or elsewhere, and/or to provide alternatives. Disclosure of Invention According to a first aspect, there is provided an inherently microporosity polymer comprising: a polymeric backbone comprising a twisted aromatic moiety, and At least one pendant group comprising carboxylic acid and oxadiazole moieties; wherein the or each side group is linked to the polymeric backbone by the oxadiazole moiety. According to a second aspect, there is provided a method of preparing an inherently microporous polymer, the method comprising: providing a precursor polymer comprising: a polymeric backbone comprising a twisted aromatic moiety (optionally as defined in the first aspect), and At least one pendant group comprising an amidoxime. (B) The precursor is added to an anhydride or an anhydride is added to the precursor. According to a third aspect there is provided a polymer of intrinsic microporosity obtainable or obtained by the method of the second aspect. According to a fourth aspect, an ion exchange membrane or resin comprising a polymer of intrinsic microporosity according to the first or third aspect. According to a fifth aspect there is provided the use of a polymer of intrinsic microporosity according to the first or third aspect in an ion exchange membrane or resin. According to a sixth aspect, there is provided an ion exchange membrane comprising a polymer having intrinsic microporosity comprising: a backbone comprising a twisted aromatic moiety, and At least one pendant group comprising phosphonic acid and a perfluorinated phenyl group; wherein the or each side group is attached to the backbone by the perfluorinated phenyl group. According to a seventh aspect, there is provided a battery comprising: anode, and A cathode; wherein the anode and cathode are separated by an ion exchange membrane according to the fourth or sixth aspect of the invention. According to an eighth aspect, there is provided a kit of parts for a battery, wherein the kit comprises: An anode is provided with a cathode, Cathode, and The ion exchange membrane according to the fourth or sixth aspect of the invention. According to a ninth aspect, there is provided a polymer (such as an inherently microporous polymer) comprising: a polymeric backbone comprising a twisted aromatic moiety, and At least one of the pendant groups comprises: ;;;, Or (b) Wherein R is an aliphatic or aromatic carboxylic acid group; wherein p is 1 to 100; Wherein G 1 is C (NH 2) =noh, C (=o) OH or S (=o) 2 OH; wherein G 2 is S (=o) 2 OH; ; Or (b) 。 According to a tenth aspect, there is provided a polymer (such as an inherently microporous polymer) comprising: a polymeric backbone comprising a twisted aromatic moiety, and At least one of the pendant groups comprises: ; Wherein the or each side group is attached to the polymeric backbone; And wherein the polymeric backbone further comprises As moieties suspended thereby (optionally wherein the moieties are bet