Composite polyamide membrane post-treated with nitrous acid

Patent metadata

Field	Value
Publication number	US-9943810-B2
Application number	US-201515301981-A
Country	US
Kind code	B2
Filing date	May 5, 2015
Priority date	May 14, 2014
Publication date	Apr 17, 2018
Grant date	Apr 17, 2018

Abstract

A method for making a composite polyamide membrane comprising a porous support and a polyamide layer, including the steps of: i) applying a polar solution comprising a polyfunctional amine monomer and a non-polar solution comprising a polyfunctional acyl halide monomer to a surface of a porous support and interfacially polymerizing the monomers to form a polyamide layer; and ii) exposing the thin film polyamide layer to nitrous acid; wherein the method is characterized by at least one of: conducting the interfacial polymerization of step i) in the presence of a subject amine compound, or applying a subject amine compound to the interfacially polymerized polyamide layer prior to step ii), wherein the subject amine compound is different from the polyfunctional acyl halide and polyfunctional amine monomers.

First claim

The invention claimed is:

1. A method for making a composite polyamide membrane comprising a porous support and a polyamide layer, wherein the method comprises the steps of:
i) applying a polar solution comprising a polyfunctional amine monomer and a non-polar solution comprising a polyfunctional acyl halide monomer to a surface of a porous support and interfacially polymerizing the monomers to form a polyamide layer; and
ii) exposing the polyamide layer to nitrous acid; wherein the method is characterized by:
applying a subject amine compound to the interfacially polymerized polyamide layer prior to step ii) such that the subject amine compound reacts with residual acid chloride groups present on the surface of the polyamide layer,

wherein the subject amine compound is different from the polyfunctional amine monomer and is represented by the following formula:

wherein:
Z is: hydroxyl, alkoxy, ester, secondary or tertiary amine, or keto-amide;
Y is: hydrogen, carboxylic acid, sulfonic acid or salt thereof, halogen, amine or an alkyl group having from 1 to 12 carbon atoms; and
A, A′, A″ and A′″ are independently: Z, hydrogen, or amine with the proviso that at least one of A, A′, A″ and A′″ is a primary or secondary amine and that at least one of Y, A or A″ is hydrogen.

2. The method of claim 1 wherein Z and at least one of A′ or A′″ is hydroxyl with the proviso that at least one of A or Y is hydrogen.

3. The method of claim 1 wherein Z and at least one of A′ or A′″ is a secondary or tertiary amine with the proviso that at least one of A or Y is hydrogen.

4. The method of claim 1 wherein: Z is: hydroxyl or methoxy; Y is: hydrogen, halogen or carboxylic acid; and A, A′, A″ and A′″ are independently: hydrogen or amine with the proviso that at least one of A, A′, A″ and A′″ is a primary or secondary amine and that at least one of A or A″ is hydrogen.

5. The method of claim 1 wherein: Z is hydroxyl, A′ is hydroxyl, and A is hydrogen provided at least one of A″, A′″ or Y is a primary or secondary amine.

6. The method of claim 1 wherein: Z is hydroxyl, A′″ is hydroxyl, and Y is hydrogen provided at least one of A, A′ or A″ is a primary or secondary amine.

7. The method of claim 1 wherein the polyfunctional amine is a difunctional amine.

8. The method of claim 1 wherein at least one of the polar and non-polar solutions further comprises a tri-hydrocarbyl phosphate compound represented by following formula:

wherein R 1 , R 2 and R 3 are independently: hydrogen or hydrocarbyl groups comprising from 1 to 10 carbon atoms, with the proviso that no more than one of R 1 , R 2 and R 3 are hydrogen.

9. The method of claim 1 wherein the subject amine compound comprises at least one of: 3,5-diaminophenol, 2,4-diaminophenol, 3-aminophenol, 2-aminophenol, 4-aminophenol, 5-aminobenzene-1,3-diol, 3-amino-5-hydroxybenzoic acid, 3-amino-5-hydroxybenzenesulfonic acid, 5-methoxybenzene-1,3-diamine, 4-methoxybenzene-1,3-diamine, 3-methoxyaniline, 2-methoxyaniline, 4-methoxyaniline, 3-amino-5-methoxybenzoic acid, 3-amino-5-methoxybenzenesulfonic acid, N1,N1-dimethylbenzene-1,3-diamine, N1,N1-dimethylbenzene-1,3,5-triamine, N1,N1,N3,N3-tetramethylbenzene-1,3,5-triamine,N,N′-(5-amino-1,3-phenylene)bis(3-oxobutanamide), N-(4-amino phenyl)-3-oxobutanamide, 5-amino-1,3-phenylene bis(2,2,2-trifluoroacetate), 5-amino-1,3-phenylene diacetate, 3,5-bis((tert-butyldimethylsilyl)oxy)aniline, (3,5-bis((tert-butyldimethylsilyl)oxy) phenyl)methanamine, and 2-(3,5-bis((tert-butyldimethylsilyl)oxy) phenyl)ethanamine.

10. A method for making a composite polyamide membrane comprising a porous support and a polyamide layer, wherein the method comprises the steps of:
i) applying a polar solution comprising a polyfunctional amine monomer and a non-polar solution comprising a polyfunctional acyl halide monomer to a surface of a porous support and interfacially polymerizing the monomers to form a polyamide layer; and
ii) exposing the polyamide layer to nitrous acid; wherein the method is characterized by applying a subject amine compound to the interfacially polymerized polyamide layer prior to step ii) such that the subject amine compound reacts with residual acid chloride groups present on the surface of the polyamide layer,
wherein the subject amine compound is different from the polyfunctional amine monomer and is represented by the following formula:

wherein:
Z is: hydroxyl, alkoxy, ester, secondary or tertiary amine or keto-amide;
Y is: hydrogen, carboxylic acid, sulfonic acid or salt thereof, halogen, amine or an alkyl group having from 1 to 12 carbon atoms; and
A, A′, A″ and A′″ are independently: Z, hydrogen, or amine with the proviso that at least one of A, A′, A″ and A′″ is a primary or secondary amine and that at least one of Y, A or A″ is hydrogen; and wherein at least one of the polar and non-polar solutions further comprises a tri-hydrocarbyl phosphate compound represented by following formula:

wherein R 1 , R 2 and R 3 are independently: hydrogen or hydrocarbyl groups comprising from 1 to 10 carbon atoms, with the proviso that no more than one of R 1 , R 2 and R 3 are hydrogen.

Assignees

• Dow Global Technologies Llc

Inventors

• Paul Mou
• Jansma Matthew J
• Roy Abhishek
• Tomlinson Ian A

Classifications

• B01D67/0088

  Physical treatment with compounds, e.g. swelling, coating or impregnation · CPC title

• B01D67/0006 Primary

  by chemical reactions (in-situ polymerisation, polycondensation, cross-linking or reaction for manufacturing composite membranes B01D69/125) · CPC title

• B05D3/108

  Curing · CPC title

• B01D61/002

  Forward osmosis or direct osmosis · CPC title

• B01D2323/40

  in-situ membrane formation · CPC title