Granted Patent B2

US 9,808,769 · App. 15/030,919 · Granted Nov 7, 2017

Abstract

Claims (35)

1. A method for making a composite polyamide membrane comprising a porous support and a thin film polyamide layer, wherein the method comprises:

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 thin film polyamide layer;

ii) treating the thin film polyamide layer with a polyfunctional arene compound comprising 1 or 2 benzene rings collectively substituted with the follow four functional groups:

(a) a first functional group (w) selected from the group consisting of: —NR 4 R 5 and —OH,

(b) a second functional group (x) selected from the group consisting of: —NR 4 R 5 , —OH, —COOH, and-SO 3 H,

(c) a third functional group (y) is selected from the group consisting of: —H, —NR 4 R 5 , —OH, —COOH, and —SO 3 H,

(d) a fourth functional group (z) selected from the group consisting of: —H, —CH 3 , —NR 4 R 5 , —OH, —COOH and —SO 3 H,

wherein: (R 4 ) and (R 5 ) are independently selected from the group consisting of: —H and hydrocarbyl groups comprising from 1 to 10 carbon atoms; and

iii) exposing the thin film polyamide layer to nitrous acid;

wherein step ii) may occur before, during or after step iii) and, wherein the method is characterized by:

(A) at least one of the polar and non-polar solutions further comprises a tri-hydrocarbyl phosphate compound represented by Formula I:

wherein R 1 , R 2 and R 3 are independently selected from the group consisting of: hydrogen and 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; and

(B) the non-polar solution further comprises an acid-containing monomer comprising a C 2 -C 20 hydrocarbon moiety substituted with at least one carboxylic acid functional group or salt thereof and at least one amine-reactive functional group selected from the group consisting of: acyl halide, sulfonyl halide and anhydride, wherein the acid-containing monomer is distinct from the polyfunctional acyl halide monomer.

2. The method of claim 1 wherein the polyfunctional arene compound is represented by at least one of:

wherein (L) is selected from the group consisting of: a bond between the rings, an alkylene group comprising from 1 to 6 carbon atoms and an oxyalkylene group comprising from 1 to 6 carbon atoms.

3. The method of claim 1 wherein the non-polar solution comprises an acid-containing monomer which comprises an arene moiety.

4. The method of claim 1 wherein the non-polar solution comprises an acid-containing monomer that comprises an aliphatic moiety.

5. The method of claim 1 wherein the non-polar solution comprises an acid-containing monomer that comprises at least two amine-reactive functional groups.

6. The method of claim 1 wherein the thin film polyamide layer has a dissociated carboxylic acid content of at least 0.18 moles/kg at pH 9.5 as measured by Rutherford Backscattering prior to the step of exposing the thin film polyamide layer to nitrous acid.

7. The method of claim 1 wherein:

(w) is selected from the group consisting of: —NR 4 R 5 and —OH,

(x) is selected from the group consisting of: —COOH and —SO 3 H,

(y) is selected from the group consisting of: —H, —COOH and —SO 3 H,

(z) is selected from the group consisting of: —H, —CH 3 , —COOH, and —SO 3 H, and

(R 4 ) and (R 5 ) are independently selected from the group consisting of: —H and hydrocarbyl groups comprising from 1 to 10 carbon atoms.

8. The method of claim 1 wherein:

(w) is selected from the group consisting of: —NR 4 R 5 ,

(x) is selected from the group consisting of: —OH,

(y) selected from the group consisting of: —H, —COOH, and —SO 3 H,

(z) selected from the group consisting of: —H, —CH 3 , —COOH, and —SO 3 H, and

(R 4 ) and (R 5 ) are independently selected from the group consisting of: —H and hydrocarbyl groups comprising from 1 to 10 carbon atoms.

9. The method of claim 1 wherein:

(w) and (x) are selected from the group consisting of: —NR 4 R 5 ,

(y) and (z) are selected from the group consisting of: —H, and

(R 4 ) and (R 5 ) are independently selected from the group consisting of: —H and hydrocarbyl groups comprising from 1 to 10 carbon atoms.

Assignments (7)