High molecular weight polythioaminals from a single monomer

Patent metadata

Field	Value
Publication number	US-9765188-B2
Application number	US-201615287419-A
Country	US
Kind code	B2
Filing date	Oct 6, 2016
Priority date	Nov 2, 2015
Publication date	Sep 19, 2017
Grant date	Sep 19, 2017

Abstract

Compounds include polythioaminals of the formula:

Each instance of R may be hydrogen or an electron withdrawing group. ‘n’ may be an integer such that the number average molecular weight (Mn) or weight average molecular weight (Mw) is between about 2,000 to about 80,000. Compounds also include polythioaminals of the formula:

Each instance of R may be independently selected from the group consisting of —H, —F, —CF 3 , and —NO 2 . Each instance of R′ may be independently selected from the group consisting of cycloalkyl, alkyl, alkylene glycol, acrylate, and siloxane. ‘n’ may be an integer such that the number average molecular weight (Mn) or weight average molecular weight (Mw) is between about 2,000 to about 80,000.

First claim

What is claimed is:

1. A method of synthesizing a polythioaminal, comprising:
mixing a thiol amine with an aldehyde to form a thiol imine; and
self-polymerizing the thiol imine to form a polythioaminal, wherein the polythioaminal has a number average molecular weight (Mn) or weight average molecular weight (Mw) between about 2,000 to about 80,000.

2. The method of claim 1 , wherein the number average molecular weight (Mn) or weight average molecular weight (Mw) of the polythioaminal is between about 15,000 to about 20,000.

3. The method of claim 1 , further comprising mixing a benzothiazole with a reducing agent to form the thiol amine.

4. The method of claim 1 , wherein the aldehyde is paraformaldehyde.

5. The method of claim 1 , further comprising adding a solvent selected from the group consisting of N-methyl-pyrrolidone, dimethylsulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, propylene carbonate, propylene glycol methyl ether acetate, methanol, ethanol, isopropanol, and acetic acid.

6. The method of claim 1 , wherein the polythioaminal is of the formula:

wherein each instance of R is an electron withdrawing group, and wherein n is an integer, and the polythioaminal has a number average molecular weight (Mn) or weight average molecular weight (Mw) between about 2,000 to about 80,000.

7. The method of claim 1 , wherein the polythioaminal is of the formula:

wherein each instance of R is independently selected from the group consisting of —H, —F, —CF 3 , and —NO 2 , wherein each instance of R′ is independently selected from the group consisting of cycloalkyl, alkyl, alkylene glycol, acrylate, and siloxane, and wherein n is an integer, and the polythioaminal has a number average molecular weight (Mn) or weight average molecular weight (Mw) between about 2,000 to about 80,000.

8. The method of claim 1 , wherein the thiol amine is an aminothiophenol or an aliphatic amino thiol.

9. The method of claim 1 , further comprising contacting the thiol imine with an amine-substituted substrate.

10. A method of synthesizing a polythioaminal, comprising:
mixing an aminothiophenol or aliphatic amino thiol with an aldehyde to form a thiol imine; and
self-polymerizing the thiol imine to form a polythioaminal, wherein the polythioaminal has a number average molecular weight (Mn) or weight average molecular weight (Mw) between about 2,000 to about 80,000.

11. The method of claim 10 , further comprising mixing a benzothiazole with a reducing agent to form the aminothiophenol.

12. The method of claim 10 , wherein the aldehyde is paraformaldehyde.

13. The method of claim 10 , further comprising adding a solvent selected from the group consisting of N-methyl-pyrrolidone, dimethylsulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, propylene carbonate, propylene glycol methyl ether acetate, methanol, ethanol, isopropanol, and acetic acid.

14. The method of claim 10 , further comprising contacting the thiol imine with an amine-substituted substrate.

15. A method of synthesizing a polythioaminal, comprising:
mixing an aminothiophenol with paraformaldehyde to form a thiol imine; and
self-polymerizing the thiol imine to form a polythioaminal, wherein the polythioaminal has a number average molecular weight (Mn) or weight average molecular weight (Mw) between about 2,000 to about 80,000, and the polythioaminal is of the formula:

wherein each instance of R is an electron withdrawing group, and wherein n is an integer.

16. The method of claim 15 , wherein R is, independently in each instance, —F, —CF 3 , —NO 2 , —Cl, —Br, —I, or nitrile.

17. The method of claim 15 , further comprising contacting the thiol imine with an amine-substituted substrate.

Assignees

• IBM

Inventors

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

Classifications

• C08G75/0236

  containing atoms other than carbon or sulfur in a linkage between arylene groups · CPC title

• C08G75/0272 Primary

  using other sulfur sources · CPC title

• C08G75/04

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