Ionic polyamide and polyamide-imide materials and methods of use

Patent metadata

Field	Value
Publication number	US-10836865-B2
Application number	US-201815896513-A
Country	US
Kind code	B2
Filing date	Feb 14, 2018
Priority date	Feb 14, 2017
Publication date	Nov 17, 2020
Grant date	Nov 17, 2020

Abstract

Disclosed are compositions and methods of preparing ionic polyamides. Also disclosed are compositions and methods of preparing ionic polyamide-imides. Additionally, disclosed herein are compositions comprising the ionic polyamides or polyamide-imides. The compositions comprising the ionic polyamides or polyamide-imides can include an ionic liquid. The disclosed polyamides and polyamide-imides can be utilized for three-dimensional printing or to capture gases.

First claim

What is claimed is:

1. A composition, comprising an ionic polyamide having the formula (I):

wherein,
L 1 is, independently for each occurrence, selected from the group consisting of a bond, a substituted or unsubstituted C 1-20 alkyl, a substituted or unsubstituted C 2-20 alkenyl, a substituted or unsubstituted C 2-20 alkynyl, a substituted or unsubstituted C 1-20 heteroalkyl, a substituted or unsubstituted C 2-20 heteroalkenyl, a substituted or unsubstituted C 2-20 heteroalkynyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted heterocycloalkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a polyester, a polyalkyleneoxy, and combinations thereof;
L 2 and L 3 are independently selected from the group consisting of a substituted or unsubstituted C 1-20 alkyl, a substituted or unsubstituted C 2-20 alkenyl, a substituted or unsubstituted C 2-20 alkynyl, a substituted or unsubstituted C 1-20 heteroalkyl, a substituted or unsubstituted C 2-20 heteroalkenyl, a substituted or unsubstituted C 2-20 heteroalkynyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted heterocycloalkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, and combinations thereof;
Q is an ionized heteroaryl, an ionized heterocycloalkyl, or an ionized heteroalkyl;
A is an anion; and
n is an integer from 2 to 100,000.

2. The composition of claim 1 , wherein
L 1 is, independently for each occurrence, selected from the group consisting of a bond, a C 1-20 alkyl, a C 2-20 alkenyl, a C 1-20 heteroalkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a polyalkyleneoxy, and combinations thereof; and
L 2 and L 3 are independently selected from the group consisting of a C 1-20 alkyl, a C 2-20 alkenyl, a C 2-20 alkynyl, a C 1-20 heteroalkyl, a C 2-20 heteroalkenyl, a C 2-20 heteroalkynyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted heterocycloalkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, and combinations thereof.

3. The composition of claim 1 , wherein L 1 is, independently for each occurrence, a branched or unbranched C 1-12 alkyl, a polyethyleneoxy, a polypropyleneoxy, or a substituted or unsubstituted aryl.

4. The composition of claim 1 , wherein L 2 is a branched or unbranched C 1-12 alkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl.

5. The composition of claim 1 , wherein L 3 is a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted heterocycloalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl.

6. The composition of claim 1 , wherein Q is an ionized heteroaryl selected from the group consisting of substituted or unsubstituted pyrazolium, substituted or unsubstituted pyridinium, substituted or unsubstituted pyrazinium, substituted or unsubstituted pyrimidinium, substituted or unsubstituted pryidazinium, substituted or unsubstituted piperidinium, substituted or unsubstituted pyrrolidinium, substituted or unsubstituted indolizinium, substituted or unsubstituted isoindolium, substituted or unsubstituted indolium, substituted or unsubstituted indazolium, substituted or unsubstituted imidazolium, substituted or unsubstituted oxazolium, substituted or unsubstituted triazolium, substituted or unsubstituted tetrazolium, substituted or unsubstituted thiazolium, substituted or unsubstituted purinium, substituted or unsubstituted isoquinolinium, substituted or unsubstituted quinolinium, substituted or unsubstituted phthalazinium, substituted or unsubstituted quinooxalinium, substituted or unsubstituted phenazinium, and substituted or unsubstituted morpholininium.

7. The composition of claim 1 , wherein Q is an ionized heteroalkyl comprising a C 3 -C 20 substituted or unsubstituted ammonium or a C 3 -C 20 substituted or unsubstituted phosphonium group.

8. The composition of claim 1 , wherein A is selected from chloride, bromide, iodide, nitrate, dicyanamide, acetate, bis(trifluoromethane)sulfonimide, hexafluorophosphate, tetrafluoroborate, sulfate, phosphate, tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride, thiocyanide, mesylate, triflate, or tosylate.

9. The composition of claim 1 , wherein the ionic polyamide is selected from the group consisting of:

wherein,
L 1 is, independently for each occurrence, selected from the group consisting of a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted heterocycloalkyl, a substituted or unsubstituted aryl, and a substituted or unsubstituted heteroaryl;
L 2 is selected from the group consisting of a substituted or unsubstituted C 1-20 alkyl, a substituted or unsubstituted C 2-20 alkenyl, a substituted or unsubstituted C 2-20 alkynyl, a substituted or unsubstituted C 1-20 heteroalkyl, a substituted or unsubstituted C 2-20 heteroalkenyl, a substituted or unsubstituted C 2-20 heteroalkynyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted heterocycloalkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, and combinations thereof;
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are hydrogen; and
wherein n is an integer from 2 to 100,000.

10. The composition of claim 1 , further comprising an ionic liquid.

11. A three-dimensional printable resin composition comprising the ionic polyamide composition of claim 1 and a carrier.

12. A method for synthesizing an ionic polyamide according to claim 1 , comprising:
(i) reacting a diacid and an amine containing compound, wherein the amine containing compound comprises an amine functional group and an ionizable hetero-functional group, to generate a bridging monomer; and
(ii) reacting the bridging monomer and an alkylating agent, wherein the alkylating agent ionizes the ionizable hetero-functional group.

13. The method of claim 12 , wherein the ionizable hetero-functional group is selected from an ionizable heteroaryl functional group, an ionizable heterocycloalkyl functional group, or an ionizable heteroalkyl functional group.

14. The method of claim 12 , wherein the amine containing compound comprises an ionizable heteroaryl functional group selected from imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, pyridine, pyrimidine, piperidine, pyrrolidine, or pyrazole.

15. The method of claim 12 , wherein the diacid is selected from terephthaloyl chloride, oxalyl chloride, malonyl chloride, succinyl chloride, glutaryl chloride, adipoyl chloride, pimeloyl chloride, suberoyl chloride, azelaoyl chloride, sebacoyl chloride, isophthaloyl chloride, or mixtures thereof.

16. A composition comprising an ionic polyamide selected from the group consisting of:

wherein
L 2 is a bond, CH 2 , C(O), O, S, SO 2 , substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 alkynyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 2-20 heteroalkenyl, substituted or unsubstituted C 2-20 heteroalkynyl, substi

Assignees

• Univ Alabama

Inventors

• Bara Jason Edward
• O'Harra Kathryn E

Classifications

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• C08G69/26

  derived from polyamines and polycarboxylic acids · CPC title

• B01D71/58

  Other polymers having nitrogen in the main chain, with or without oxygen or carbon only · CPC title

• C08G73/10

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title

• C08G73/14 Primary

  Polyamide-imides · CPC title