Methods of manufacturing poly(hexahydrotriazine)s via suspension or emulsion polymerization

Patent metadata

Field	Value
Publication number	US-2016289387-A1
Application number	US-201514674213-A
Country	US
Kind code	A1
Filing date	Mar 31, 2015
Priority date	Mar 31, 2015
Publication date	Oct 6, 2016
Grant date	—

Abstract

A method of manufacturing a hemiaminal dynamic covalent network (HDCN) comprises reacting a diamine and formaldehyde in the presence of a reaction medium comprising a polar solvent and a nonpolar solvent at a temperature of about 15° C. to about 100° C. to form the HDCN. A composition comprising the produced HDCN can be molded to form various articles comprising poly(hexahydrotriazine)s.

First claim

What is claimed is:

1 . A method of manufacturing a hemiaminal dynamic covalent network, the method comprising:
reacting a diamine and formaldehyde in the presence of a reaction medium comprising a first solvent and an immiscible second solvent at a temperature of about 15° C. to about 100° C. to form the hemiaminal dynamic covalent network.

2 . The method of claim 1 , wherein the first solvent is a polar solvent comprising one or more of the following: 1-methyl-2-pyrrolidone; N,N-dimethyl formamide; N,N-dimethyl acetamide; dimethyl sulfoxide;
hexamethylphosphoramide; diphenyl sulfone; or tetramethylene sulfone.

3 . The method of claim 1 , wherein the immiscible second solvent is a nonpolar solvent comprising one or more of the following: benzene; toluene; xylenes; diethyl benzene; C5-C20 alkanes; or diethyl ether.

4 . The method of claim 3 , wherein the immiscible second solvent is a paraffinic hydrocarbon.

5 . The method of claim 1 , wherein the volume ratio of the first solvent relative to the immiscible second solvent is about 1:1 to about 1:5.

6 . The method of claim 1 , wherein the reaction medium further comprises water.

7 . The method of claim 1 , wherein the reaction medium further comprises one or more of a surfactant; or a stabilizer.

8 . The method of claim 7 , wherein the surfactant comprises sorbitan esters.

9 . The method of claim 7 , wherein the stabilizer comprises amphiphilic copolymers.

10 . The method of claim 1 , wherein the reaction is conducted in an emulsion or a suspension.

11 . The method of claim 1 , wherein the diamine is 4,4′-oxydianiline, 4,4′-diaminodiphenylmethane, 3,3 ′-methylenedianiline, or 4-aminophenyl sulfone.

12 . The method of claim 1 , further comprising obtaining a powder of the hemiaminal dynamic covalent network by spray drying.

13 . The method of claim 1 , further comprising contacting a reaction product comprising the hemiaminal dynamic covalent network, the first solvent, and the second solvent with a polar protic solvent to precipitate the hemiaminal dynamic covalent network; and filtering the precipitated hemiaminal dynamic covalent network.

14 . The method of claim 12 , further comprising drying the filtered hemiaminal.

15 . A method of manufacturing a hemiaminal dynamic covalent network, the method comprising:
combining a polar phase with a nonpolar phase; the polar phase comprising a diamine, formaldehyde, and a polar solvent; and the nonpolar phase comprising a nonpolar solvent to form an emulsion or a suspension; and reacting the diamine with formaldehyde in the emulsion or suspension to form the hemiaminal dynamic covalent network.

16 . The method of claim 14 , wherein the polar phase further comprises water.

17 . The method of claim 14 , wherein the nonpolar phase further comprises one or more of a surfactant or a stabilizer.

18 . The method of claim 14 , wherein the volume ratio of the polar phase relative to the nonpolar phase is about 1:1 to about 1:5.

19 . A method of manufacturing an article comprising a poly(hexahydrotriazine), the method comprising:
providing a composition comprising a hemiaminal dynamic covalent network manufactured according to the method of claim 1 , and molding the composition to form an article comprising a poly(hexahydrotriazine).

20 . A method of manufacturing an article comprising a poly(hexahydrotriazine), the method comprising:
providing a composition comprising a hemiaminal dynamic covalent network manufactured according to the method of claim 15 , and molding the composition to form an article comprising a poly(hexahydrotriazine).

Assignees

• Wang Xiao
• Sadana Anil K
• Khatiwada Suman
• Baker Hughes Inc

Inventors

• Wang Xiao
• Sadana Anil K
• Khatiwada Suman

Classifications

• C08G12/08 Primary

  aromatic · CPC title

• C08G73/065 Primary

  Preparatory processes · CPC title

• C08J2379/04

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title

• C08G73/0644

  Poly(1,3,5)triazines · CPC title

• C08J3/12

  Powdering or granulating · CPC title