Composite membrane and method for making the same

• US 6,337,018 B1
• Filed: 04/17/2000
• Issued: 01/08/2002
• Est. Priority Date: 04/17/2000
• Status: Expired due to Term

• Current Assignee: Dow Global Technologies LLC (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Mickols, William E.
• Primary Examiner(s): FORTUNA, ANA M
• Application Number:
  US09/550,527
• Time in Patent Office: 631 Days
• Field of Search: 210/490, 210/500.38, 210/500.37, 210/500.27, 210/500.23, 264/48, 264/49, 427/244
• US Class Current: 210/500.38
• CPC Class Codes: B01D 69/1251 by interfacial polymerisation
• CPC Class Codes: B01D 71/56 Polyamides, e.g. polyester-amides

Abstract

A composite membrane and method for making the same, comprising a porous support and a crosslinked polyamide surface. The subject membrane provides improved flux and/or rejection rates. The subject membrane is further capable of operating at lower operating pressures. The subject method includes reacting a polyfunctional amine with a polyfunctional acyl halide to form a polyamide. The method includes the step of contacting a phosphorous containing compound with the polyfunctional acyl halide prior to and/or during the reaction between the polyfunctional acyl halide and a polyfunctional amine. The subject process is easily adapted to commercial scale manufacturing processes and is particularly suited for making nanofiltration and reverse osmosis composite membranes.

Claims

1. A method for making a composite membrane comprising the non-sequential steps of coating a porous support with:

(i) a solution containing a polyfunctional amine and (ii) a solution containing a polyfunctional acyl halide, wherein the polyfunctional amine and polyfunctional acyl halide are contacted with each other and react to form a polyamide layer on the porous support, the process being characterized by the step of contacting a phosphorous containing compound with the polyfunctional acyl halide prior to the reaction between the polyfunctional acyl halide and polyfunctional amine wherein the phosphorous containing compound has a solubility parameter of from about 15 to about 26 J^½

cm<sup>−

{fraction (3/2)}</sup>.

2. The method of claim 1 wherein the phosphorous containing compound is contacted with the polyfunctional acyl halide prior to the step of contacting the polyfunctional acyl halide and polyfunctional amine.

3. The method of claim 2 wherein the polyfunctional acyl halide solution comprises from 0.001 to 10 weight volume percent of the phosphorous containing compound.

4. The method of claim 1 wherein the phosphorous containing compound is substantially soluble in the polyfunctional acyl halide solution.

5. The method of claim 1 wherein the phosphorous containing compound has an energy of interaction with the polyfunctional acyl halide of greater than about 4.0 kcal/Mole.

6. The method of claim 1 wherein the phosphorous containing compound is reacted with the polyfunctional acyl halide prior to and/or during the step of contacting the polyfunctional amine and polyfunctional acyl halide such that the resulting polyamide layer comprises a detectable quantity of retained phosphorous.

7. The method of claim 1 wherein the phosphorous containing compound comprises at least one of:

phosphates, phosphites, phosphines, phosphine oxides, phosphonates, diphosphonates, phosphinates, phosphinites, phosphonites, pyrophosphates, pyrophosphoramides, phosphor amides, phosphorothionates, phosphorodithionates, and phosphoroamido thionates.

8. The method of claim 1 wherein the phosphorous containing compound comprises a compound represented by the formula:

wherein Z is the same or different and is selected from;

X, O—

P—

(X)₂, P(O)—

X₂, (P(—

X))_m—

P—

X₂, (O—

P(—

X))_m—

O—

P—

X₂, (P(O)(—

X))_m—

P(O)—

X₂, and (O—

P(O)(—

X))_m—

O—

P(O)—

X₂;

P is phosphorous, O is oxygen, m is an integer from 1 to 5;

Y is O or a non-bonded pair of electrons, X is the same or different and is selected from;

R and R including one or more oxygen linkage(s), and R is the same or different and is selected from H (hydrogen), and a carbon containing moiety.

9. The method of claim 8 wherein Z is selected from C₁-C₈ aliphatic groups.

10. The method of claim 8 wherein at least one Z is selected from an aromatic group.

11. The method of claim 8 wherein Y is oxygen and Z is the same or different and is selected from R and R including one or more oxygen linkages;

and R is the same or different and is selected from;

H and C₁-C₁₂ containing moiety.

12. The method of claim 11 wherein R is selected from C₁-C₈ aliphatic groups.

13. The method of claim 11 wherein the phosphorous containing compound comprises a compound represented by the formula:

14. The method of claim 13 wherein R is selected from C₁-C₈ aliphatic groups.

15. The method of claim 13 wherein at least one R is selected from an aromatic group.

16. The method of claim 11 wherein at least one R is selected from an aromatic group.

17. The method of claim 8 wherein Y is a non-bonded pair of electrons and the phosphorous containing compound comprises a compound represented by the formula:

wherein Z is the same or different and is selected from R and R including one or more oxygen linkages; and

R is the same or different and is selected from;

H and C₁-C₁₂ containing moiety.

18. The method of claim 17 wherein R is selected from C₁-C₈ aliphatic groups.

19. The method of claim 17 wherein at least one R is selected from an aromatic group.

20. The method of claim 17 wherein Z is the same or different and is selected from O—

R and R.

21. The method of claim 20 wherein R is selected from C₁-C₈ aliphatic groups.

22. The method of claim 20 wherein at least one R is selected from an aromatic group.

23. The method of claim 1 wherein the polyfunctional amine comprises metaphenylene amine and the polyfunctional acyl halide comprises trimesoyl chloride.

24. The method of claim 23 wherein the polyfunctional amine solution is an aqueous solution and the polyfunctional acyl halide solution is an organic solution.

25. The method of claim 1 wherein the polyamide layer is contacted with a solution containing from 200 to 10,000 ppm of hypochlorite ion at a pH of at least 10.5.

26. The method of claim 25 wherein the polyamide layer is heat treated by contact with water at a temperature of 40°

C. to 100°

C. before contacting the membrane solution with the containing hypochlorite ion.

27. The method of claim 1 wherein the polyamide layer is contacted with an amine selected from the groups consisting of:

ammonia, substituted ammonia, butylamine, cyclohexylamine, and 1,6 hexane diamine.

28. The method of claim 1 wherein the polyamide layer is contacted with a strong mineral acid.

29. A membrane made according to the method of claim 1.

30. A method for making a composite membrane comprising the steps of coating a porous support with an aqueous solution containing a polyfunctional amine followed by subsequently coating an organic solution containing a polyfunctional acyl

halide such that the polyfunctional amine and polyfunctional acyl halide are contacted with each other and react to form a polyamide layer on the porous support, the process being characterized by the step of including from 0.001 to 10 weight volume percent of a non-pyrophoric phosphorous containing compound within the polyfunctional acyl halide solution, wherein the phosphorous containing compound has a solubility parameter of from about 15 to about 26 J^½

cm<sup>−

{fraction (3/2)}</sup>, an energy of interaction with the polyfunctional acyl halide of greater than 4.0 kcal/Mole and is represented by the formula;

wherein Z is the same or different and is selected from;

X, O—

P—

(X)₂, P(O)—

X₂, (P(—

X))_m—

P—

X₂, (O—

P(—

X))_m—

O—

P—

X₂, (P(O)(—

X))_m—

P(O)—

X₂, and (O—

P(O)(—

X))_m—

O—

P(O)—

X₂;

P is phosphorous, O is oxygen, m is an integer from 1 to 5;

Y is O or a non-bonded pair of electrons, X is the same or different and is selected from;

R and R including one or more oxygen linkage(s), and R is the same or different and is selected from H (hydrogen), and a C₁-C₁₂ containing moiety.