Functionalization of Diels-Alder polyphenylene polymers

Patent metadata

Field	Value
Publication number	US-10053534-B2
Application number	US-201715398545-A
Country	US
Kind code	B2
Filing date	Jan 4, 2017
Priority date	Jan 4, 2016
Publication date	Aug 21, 2018
Grant date	Aug 21, 2018

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 (II):

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 perfluoroalkyl, optionally substituted C 1-12 heteroalkyl, halo, 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 perfluoroalkyl, optionally substituted C 1-12 heteroalkyl, 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 h is, independently, an integer of from 0 to 5, wherein at least one h is not 0;
m is an integer of from about 1 to 1000; and
wherein at least one R H on a pendent group of formula (II) comprises a substituted aryl group comprising halo or alkoxy or aryloxy.

2. The composition of claim 1 , wherein:
at least one R H is —L H —Ar H ;
L H is a covalent bond, carbonyl, oxy, thio, azo, phosphonoyl, phosphoryl, sulfonyl, sulfinyl, sulfonamide, imino, imine, phosphine, 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, or optionally substituted C 4-18 aryleneoxy; and
Ar H is an optionally substituted aryl.

3. The composition of claim 2 , 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.

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

or a salt thereof, wherein:
L H is a covalent bond, carbonyl, oxy, thio, azo, phosphonoyl, phosphoryl, sulfonyl, sulfinyl, sulfonamide, imino, imine, phosphine, 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, or optionally substituted C 4-18 aryleneoxy; and
Ar H is an optionally substituted aryl.

5. The composition of claim 1 , wherein at least one R H is an optionally substituted C 4-18 aryl, optionally substituted C 1-6 alk-C 4-18 aryl, optionally substituted C 4-18 aryl-C 1-6 alkoxy, optionally substituted C 4-18 aryloxy, optionally substituted C 5-19 aryloxycarbonyl, optionally substituted C 5-19 aryloyl, optionally substituted C 4-18 arylcarbonyl-C 1-6 alkyl, optionally substituted C 4-18 arylsulfonyl, or optionally substituted C 4-18 arylsulfonyl-C 1-6 alkyl; and/or wherein at least one R H is optionally substituted C 4-18 aryloxy comprising one or more halo or haloalkyl.

6. The composition of claim 5 , wherein each and every R H comprises a substituted aryl group.

7. The composition of claim 1 , wherein:
R S is —SO 2 —R S1 or —SO 2 —NR N1 —R S2 or —SO 2 —NR N1 —SO 2 —R S3 , wherein each R S1 is, independently, H, optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted perfluoroalkyl, optionally substituted aryl, optionally substituted alkaryl, or hydroxyl; each R N1 is, independently, H or optionally substituted C 1-12 alkyl, optionally substituted aryl, or optionally substituted alkaryl; each R S2 is, independently, H, hydroxyl, optionally substituted alkyl, optionally substituted alkylsulfonyl, optionally substituted aryl, or optionally substituted alkaryl; and each R S3 is, independently, H, hydroxyl, optionally substituted alkyl, optionally substituted C 1-12 haloalkyl, optionally substituted perfluoroalkyl, optionally substituted aryl, or optionally substituted alkaryl;
R P is —P(O)(OH) 2 or —O—PO(OH) 2 or —P(O)<R P1 R P2 or —P(O)<R Ar R P2 or —P(O)<R Ar R Ar , and wherein each of R P1 and R P2 is, independently, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted alkaryl, optionally substituted aryloxy, hydroxyl, or H; and each of R Ar is, independently, optionally substituted aryl, optionally substituted alkaryl, or optionally substituted aryloxy;
R C is —CO 2 H, —C(O)—R C1 , or —R CA —C(O)—R C1 , and wherein each R C1 is, independently, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted alkaryl, optionally substituted aryloxy, hydroxyl, or H; and each R CA is, independently, oxy, optionally substituted alkylene, or optionally substituted heteroalkylene; and
R F is optionally substituted aryloyl, carboxyaldehyde, optionally substituted alkanoyl, or optionally substituted alkyl.

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

9. The composition of claim 8 , wherein the optional substitution for Ar L is R H , R S , R P , R C , or R F ; and wherein the optional substitution for Ar M is R H , R S , R P , R C , R F , or a label.

10. The composition of claim 1 , wherein the composition comprises a structure having formula (IIj):

or a salt thereof, wherein:
each of Ar L and Ar M is, independently, an optionally substituted phenylene.

11. The composition of claim 1 , wherein the composition comprises a structure having any one of formulas (II-1) to (II-10) and (II-13) to (II-18):

Assignees

• Nat Tech & Eng Solutions Sandia Llc

Inventors

• Fujimoto Cy

Classifications

• 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

• C08G2261/312

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

• C08G2261/146

  Side-chains containing halogens · CPC title

• C08G2261/148

  Side-chains having aromatic units · CPC title

• C08G61/10 Primary

  only aromatic carbon atoms, e.g. polyphenylenes · CPC title