Polymers from stabilized imines

Patent metadata

Field	Value
Publication number	US-9879118-B2
Application number	US-201615249218-A
Country	US
Kind code	B2
Filing date	Aug 26, 2016
Priority date	Oct 5, 2015
Publication date	Jan 30, 2018
Grant date	Jan 30, 2018

Abstract

The disclosure describes new compositions and methods related to polyaminals and related polymers. The compositions are useful as therapeutic/drug conjugates, self-healing materials, reversible crosslinking materials, degradable hydrogels, protective coatings, and as metal scavenging agents. New atom efficient synthetic schemes are disclosed, which yield previously unobtainable high molecular weight polyaminals.

First claim

What is claimed is:

1. A method for producing a polymer, comprising:
forming a reaction mixture comprising a solvent, an aminobenzene compound, a multifunctional nucleophile, an imine forming precursor; and
heating the reaction mixture at a temperature from about 50° C. to about 150° C. to produce a polymer.

2. The method of claim 1 , wherein the aminobenzene compound comprises at least two amine groups.

3. The method of claim 1 , wherein the aminobenzene compound comprises electron withdrawing or accepting groups selected from the group consisting of: electronegative heteroatoms, positively charged groups, quaternary amine groups, conjugated groups, aromatic groups, halogens, nitriles, carbonyls, nitro groups, nitroso groups, sulfones, and sulfonates.

4. The method of claim 1 , wherein the multifunctional nucleophile comprises at least two nucleophilic groups, wherein the nucleophilic group comprises a nucleophilic atom selected from the group consisting of: C, Si, Ge, Sn, N, P, As, Sb, O, S, Se, and Te.

5. The method of claim 1 , wherein the imine forming precursor comprises a material selected from the group consisting of: formaldehyde, aqueous formaldehyde, formalin, 1,3,5-trioxane, metaformaldehyde, paraformaldehyde, glyoxylic acid, MP-glyoxylate, hexamethylentetramine, dimethoxymethane, and formyl cation equivalent.

6. The method of claim 1 , wherein the multifunctional nucleophile is a dithiol.

7. The method of claim 6 , wherein the aminobenzene compound is a difunctional aniline diimine precursor compound.

8. The method of claim 7 , wherein the difunctional aniline diimine precursor compound comprises electron withdrawing or accepting groups selected from the group consisting of: electronegative heteroatoms, positively charged groups, quaternary amine groups, conjugated groups, aromatic groups, halogens, nitriles, carbonyls, nitro groups, nitroso groups, sulfones, and sulfonates.

9. A method for producing a polymer, comprising:
forming a reaction mixture comprising a solvent, a difunctional aniline diimine precursor compound, a multifunctional nucleophile comprising at least two nucleophilic groups, wherein the nucleophilic group comprises a nucleophilic atom selected from the group consisting of: C, Si, Ge, Sn, N, P, As, Sb, O, S, Se, and Te, an imine forming precursor; and
heating the reaction mixture at a temperature from about 50° C. to about 150° C. to produce a polymer.

10. The method of claim 9 , wherein the difunctional aniline diimine precursor compound comprises electron withdrawing or accepting groups selected from the group consisting of: electronegative heteroatoms, positively charged groups, quaternary amine groups, conjugated groups, aromatic groups, halogens, nitriles, carbonyls, nitro groups, nitroso groups, sulfones, and sulfonates.

11. The method of claim 9 , wherein the imine forming precursor comprises a material selected from the group consisting of: formaldehyde, aqueous formaldehyde, formalin, 1,3,5-trioxane, metaformaldehyde, paraformaldehyde, glyoxylic acid, MP-glyoxylate, hexamethylentetramine, dimethoxymethane, and formyl cation equivalent.

12. The method of claim 9 , wherein the multifunctional nucleophile is a dithiol.

13. The method of claim 9 , wherein the difunctional aniline diimine precursor compound comprises electron withdrawing or accepting groups selected from the group consisting of: electronegative heteroatoms, positively charged groups, quaternary amine groups, conjugated groups, aromatic groups, halogens, nitriles, carbonyls, nitro groups, nitroso groups, sulfones, and sulfonates.

14. The method of claim 13 , wherein the difunctional aniline diimine precursor compound has the general structure

or the general structure

wherein R′ includes an electron withdrawing or electron accepting group, and EWG is an electron withdrawing group.

15. A method for producing a polymer, comprising:
forming a reaction mixture comprising a solvent, a difunctional aniline diimine precursor compound having the general structure

or the general structure

a multifunctional nucleophile comprising at least two nucleophilic groups, and an imine forming precursor comprising a material selected from the group consisting of: formaldehyde, aqueous formaldehyde, formalin, 1,3,5-trioxane, metaformaldehyde, paraformaldehyde, glyoxylic acid, MP-glyoxylate, hexamethylentetramine, dimethoxymethane, and formyl cation equivalent, wherein R′ includes an electron withdrawing or electron accepting group, EWG is an electron withdrawing group, and each nucleophilic group comprises a nucleophilic atom selected from the group consisting of: C, Si, Ge, Sn, N, P, As, Sb, O, S, Se, and Te; and
heating the reaction mixture at a temperature from about 50° C. to about 150° C. to produce a polymer.

16. The method of claim 15 , wherein the electron withdrawing or accepting groups are selected from the group consisting of: electronegative heteroatoms, positively charged groups, quaternary amine groups, conjugated groups, aromatic groups, halogens, nitriles, carbonyls, nitro groups, nitroso groups, sulfones, and sulfonates.

Assignees

• IBM

Inventors

• Boday Dylan J
• Garcia Jeannette M
• Hedrick James L
• Wojtecki Rudy J

Classifications

• C08G75/04 Primary

  from mercapto compounds or metallic derivatives thereof (C08G75/0204 takes precedence) · CPC title

• C08G75/02 Primary

  Polythioethers · CPC title

• C08G75/10

  from sulfur or sulfur-containing compounds and aldehydes or ketones · CPC title