Functionalization of diels-alder polyphenylene polymers

Patent metadata

Field	Value
Publication number	US-10442887-B2
Application number	US-201816039153-A
Country	US
Kind code	B2
Filing date	Jul 18, 2018
Priority date	Jan 4, 2016
Publication date	Oct 15, 2019
Grant date	Oct 15, 2019

Abstract

The present invention relates to functionalized polymers including a poly(phenylene) structure. The structure can include any useful modifications, such as the inclusion of one or more reactive handles having an aryl group. Methods and uses of such structures and polymers are also described herein.

First claim

The invention claimed is:

1. A composition comprising a structure having the formula (III) or (IV):

or a salt thereof, wherein:
each R H is, independently, H, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 haloalkyl, optionally substituted C 1-12 heteroalkyl, halo, optionally substituted C 1-12 perfluoroalkyl, optionally substituted aryl, optionally substituted alkaryl, optionally substituted arylalkoxy, optionally substituted aryloxy, optionally substituted aryloxycarbonyl, optionally substituted aryloyl, optionally substituted arylcarbonylalkyl, optionally substituted arylsulfonyl, or optionally substituted arylsulfonylalkyl;
each R 1 and R 3 is, independently, H, halo, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 haloalkyl, optionally substituted C 1-12 heteroalkyl, optionally substituted C 1-12 perfluoroalkyl, R S , R P , R C , or R F , wherein R S is an acidic moiety comprising a sulfonyl group, R P is an acidic moiety comprising a phosphoryl group, R C is an acidic moiety comprising a carbonyl group, and R F is an electron-withdrawing moiety;
each Ar L is, independently, a bivalent linker comprising optionally substituted arylene;
each Ar M is, independently, a bivalent linker comprising optionally substituted arylene;
each q is, independently, an integer of from 0 to 5;
each is, independently, an integer of from 0 to 5, wherein at least one is not 0;
each of m and n is, independently, an integer of from about 1 to 1000;
L′ is a sublink;
L is a linking segment;
Ar* is a hydrophobic segment; and
each R L is, independently, a reactive end group;
wherein at least one R H on a pendent group comprises a substituted aryl group comprising halo or alkoxy or aryloxy.

2. The composition of claim 1 , wherein L′ or L comprises a covalent bond, optionally substituted C 1-12 alkylene, optionally substituted C 1-12 alkyleneoxy, optionally substituted C 1-12 heteroalkylene, optionally substituted C 1-12 heteroalkyleneoxy, optionally substituted C 4-18 arylene, optionally substituted C 4-18 aryleneoxy, optionally substituted polyphenylene, or a structure of formula (II):

or a salt thereof.

3. The composition of claim 1 , wherein R L is optionally substituted C 7-11 aryloyl or optionally substituted C 6-18 aryl.

4. The composition of claim 1 , wherein the composition comprises a structure having the formula (IIIa) or (IIIb):

or a salt thereof; or
the formula (V) or (Va):

or a salt thereof.

5. A method comprising:
(a) providing a first composition comprising a structure having the formula (I):

or a salt thereof, wherein:
each R 1 and R 3 is, independently, H, halo, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 haloalkyl, optionally substituted C 1-12 heteroalkyl, optionally substituted C 1-12 perfluoroalkyl, R S , R P , R C , or R F , wherein R S is an acidic moiety comprising a sulfonyl group, R P is an acidic moiety comprising a phosphoryl group, R C is an acidic moiety comprising a carbonyl group, and R F is an electron-withdrawing moiety;
each Ar L is, independently, a bivalent linker comprising optionally substituted arylene;
each Ar M is, independently, a bivalent linker comprising optionally substituted arylene;
each q is, independently, an integer of from 0 to 5; and
m is an integer of from about 1 to 1000; and
(b) reacting the first composition with a reagent having the structure R H —X in the presence of a metal salt or an acid, wherein X is a leaving group and R H comprises an optionally substituted aryl group,
thereby producing a second composition comprising a structure having the formula (I) and further comprising one or more R H covalently bonded to one or more aryl rings in the structure, wherein at least one R H on a pendent group comprises a substituted aryl group comprising halo or alkoxy or aryloxy.

6. The method of claim 5 , wherein X is halo;
wherein R H is optionally substituted aryl, optionally substituted alkaryl, optionally substituted arylalkoxy, optionally substituted aryloxy, optionally substituted aryloxycarbonyl, optionally substituted aryloyl, optionally substituted arylcarbonylalkyl, optionally substituted arylsulfonyl, optionally substituted arylsulfonylalkyl, or -L H -Ar H ; and
wherein L H is a covalent bond, carbonyl, oxy, phosphonoyl, phosphoryl, sulfonyl, sulfinyl, sulfonamide, imino, nitrilo, optionally substituted C 1-12 alkylene, optionally substituted C 1-12 alkyleneoxy, optionally substituted C 1-12 heteroalkylene, optionally substituted C 1-12 heteroalkyleneoxy, optionally substituted C 4-18 arylene, optionally substituted C 4-18 aryleneoxy; and Ar H is an optionally substituted aryl.

7. The method of claim 5 , wherein the metal salt is a metal alkylsulfate, a metal alkylsulfonylamide, or a metal alkylsulfonylalkyl.

8. The method of claim 5 , wherein the metal salt comprises M[O(SO 2 —R MF )], M[N(SO 2 —R MF ) 2 ], or M[C(SO 2 —R MF ) 3 ]; wherein R MF is optionally substituted alkyl, optionally substituted aryl, optionally substituted alkaryl, optionally substituted haloalkyl, or perfluoroalkyl; and wherein M is Ag, Al, Ba, Bi, Ca, Cu, In, Re, Sc, Sn, Ti, Y, Yb, or Zn.

9. The method of claim 5 , wherein the first composition is present in a polymeric membrane.

10. The method of claim 5 , wherein the acid is a Bronsted acid or a Lewis acid.

11. The method of claim 10 , wherein the acid comprises HO(SO 2 —R AF ), HO(SO 2 F), HO(SO 2 —R Ar ), and HO(C(O)—R AF ), wherein R AF is optionally substituted alkyl, optionally substituted aryl, optionally substituted alkaryl, optionally substituted haloalkyl, or perfluoroalkyl, and wherein R Ar is optionally substituted aryl or optionally substituted alkaryl.

12. The composition of claim 1 , wherein at least one R H is -L H -Ar H ; wherein L H is a covalent bond, carbonyl, sulfonyl, —NR L3 —, —(CR L1 R L2 ) La —, —C(O)NR L3 —, —NR L3 C(O)—, —SO 2 —NR L3 —, —NR L3 —SO 2 —, —(CR L1 R L2 ) La —C(O)—NR L3 —, —(CR L1 R L2 ) La —NR L3 —C(O)—, —(CR L1 R L2 ) La —SO 2 —NR L3 —, Or —SO 2 —NR L3 —(CR L1 R L2 ) La —;
wherein each of R L1 , R L2 , and R L3 is, independently, H, optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted alkoxy, optionally substituted alkaryl, optionally substituted aryl, or halo; and
wherein Ar H is optionally substituted with one or more substituents selected from the group consisting of halo, cyano, optionally substituted haloalkyl, optionally substituted perfluoroalkyl, optionally substituted nitroalkyl, and optionally substituted alkyl.

13. The composition of claim 1 , wherein at least one R H is -L H -Ar H , wherein the Ar H is an R H1 -substituted phenyl group, and wherein R H1 is selected from the group consisting of an amino, amido, azido, nitro, nitroso, haloalkyl, and halo.

14. The composition of claim 1 , wherein Ar L , Ar M , and/or Ar* is optionally substituted phenylene, optionally substituted naphthylene, or optionally substituted phenanthrylene, and wherein Ar* is optionally substituted with one or

Assignees

• Nat Tech & Eng Solutions Sandia Llc

Inventors

• Fujimoto Cy

Classifications

• C08G2261/728

  Acylation · CPC title

• C08G2261/148

  Side-chains having aromatic units · CPC title

• C08G2261/312

  Non-condensed aromatic systems, e.g. benzene · CPC title

• C08L65/00

  Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08L7/00 - C08L57/00, C08L61/00 take precedence); Compositions of derivatives of such polymers · CPC title

• C08G2261/516

  ion-conductive · CPC title