Composite filtration membranes and methods of preparation thereof

Patent metadata

Field	Value
Publication number	US-9352286-B2
Application number	US-201414246041-A
Country	US
Kind code	B2
Filing date	Apr 5, 2014
Priority date	Sep 1, 2010
Publication date	May 31, 2016
Grant date	May 31, 2016

Abstract

A method comprises disposing, on a porous support membrane, an aqueous mixture comprising a crosslinkable polymer comprising a poly(meth)acrylate and/or poly(meth)acrylamide backbone, thereby forming an initial film layer, wherein the crosslinkable polymer comprises a side chain nucleophilic amine group capable of interfacially reacting with a multi-functional acid halide crosslinking agent to form a crosslinked polymer; contacting the initial film layer with a mixture comprising i) the multi-functional acid halide crosslinking agent, ii) an optional accelerator, and iii) an organic solvent, the organic solvent being a non-solvent for the crosslinkable polymer; and allowing the crosslinkable polymer to interfacially react with the crosslinking agent, thereby forming a composite filtration membrane comprising an anti-fouling selective layer comprising the crosslinked polymer.

First claim

What is claimed is:

1. A composite filtration membrane, comprising:
a porous support membrane layer; and
an anti-fouling selective layer disposed on the porous support membrane layer; the selective layer comprising a interfacially crosslinked polymer of formula (15):

wherein
each —R 1 is independently a hydrogen or a methyl group,
—R 2 — is a linear, branched or cyclic divalent radical selected from the group consisting of alkylenes, fluoroalkylenes, arylenes, arylalkylenes, alkylarylenes, and silicon containing groups,
—R 3 is a bridging group having a valency of m and comprising 1 to 10,000 carbons,
—X 1 — is a divalent radical selected from the group consisting of —O—, —N(H)—, and —N(R 5 )—,
—R 5 is a monovalent radical comprising 1 to 20 carbons,
m is a positive integer greater than or equal to 2,
j represents the number of bridging groups R 3 which are bound to one backbone of the crosslinked polymer, j being greater than or equal to 1,
k represents the number of backbones of the crosslinked polymer which are bound to one bridging group R 3 , k being greater than or equal to 2,
a′, b′, c′, and y′ are positive numbers,
n is a positive integer greater than 1,
—K 1 is a monovalent radical selected from the group consisting of —NH 2 — and —N(H)(R 4 )—,
—R 4 is a monovalent radical comprising 1 to 50 carbons,
—R 6 — is a divalent radical selected from the group consisting of a ethylene, 2-propylene, butylene, and combinations thereof,
—Z 1 is a monovalent radical selected from the group consisting of —H, —R 7 , -L 1 -NH 2 , -L 1 -N(H)(R 7 ), -L 1 -N(R 7 ) 2 , and hydrogen salt forms of any of the foregoing amine groups,
—R 7 is a monovalent hydrocarbon radical comprising 1 to 20 carbons,
-L 1 - is a divalent radical comprising 1 to 20 carbons,
—R 8 is a cationic monovalent radical comprising a member selected from the group consisting of quaternary amine salts, sulfonium salts, phosphonium salts, and combination thereof, wherein —R 8 has a net positive charge,
-D′-Q 1 - is a divalent linking group selected from the group consisting of amides, sulfonamides, sulfinamides, and functional groups having a phosphorous-nitrogen bond,
-Q 1 - is a divalent radical independently selected from the group consisting of —N(H)— and —N(R 4 )—,
—R 4 is a monovalent radical comprising 1 to 50 carbons, and
-D′- is a divalent radical independently selected from the group consisting of —C(═O)—, —S(═O) 2 —, and —S(═O)—, and groups comprising a phosphorous bonded to a nitrogen of -Q 1 -.

2. The composite membrane of claim 1 , wherein R 1 is methyl.

3. The composite membrane of claim 1 , wherein a′−y′>0, —R 2 — is alkylene, and —K 1 is —NH 2 .

4. The composite membrane of claim 1 , wherein —R 8 comprises a sulfonium salt.

5. The composite membrane of claim 1 , wherein —R 8 comprises a phosphonium salt.

6. The composite membrane of claim 1 , wherein —R 8 comprises a quaternary amine salt.

7. The composite membrane of claim 1 , wherein —X 1 —R 8 is

8. The composite membrane of claim 1 , wherein b′=0, and —X 1 —R 8 is

9. The composite membrane of claim 1 , wherein m=2 and R 3 -[D′] m is an isophthaloyl group:

10. The composite membrane of claim 1 , wherein a′−y′=0, —X 1 — is —O—, -D′-Q 1 - is —C(═O)—N(H)—, —R 6 — is ethylene (—CH 2 CH 2 —), and —R 8 comprises a quaternary amine salt, wherein —R 8 — has a net positive charge.

11. The composite membrane of claim 1 , wherein a′−y′=0, —X 1 — is —O—, -D′-Q 1 - is —C(═O)—N(H)—, —R 6 — is ethylene (—CH 2 CH 2 —), and —X 1 —R 8 is

12. The composite filtration membrane of claim 1 , wherein the composite membrane is suitable for ultrafiltration of an aqueous mixture.

13. The composite filtration membrane of claim 1 , wherein the selective layer has a thickness of greater than 0 nm and less than or equal to 50 nm.

14. A composite filtration membrane, comprising:
a porous support membrane layer; and
an anti-fouling selective layer disposed on the porous support membrane layer; the selective layer comprising a interfacially crosslinked polymer of formula (16):

wherein
each —R 1 is independently a hydrogen or a methyl group,
—R 2 — is a linear, branched or cyclic divalent radical selected from the group consisting of alkylenes, fluoroalkylenes, arylenes, arylalkylenes, alkylarylenes, and silicon containing groups,
—R 3 is a bridging group having a valency of m and comprising 1 to 10,000 carbons,
—X 1 — is a divalent radical selected from the group consisting of —O—, —N(H)—, and —N(R 5 )—,
—R 5 is a monovalent radical comprising 1 to 20 carbons,
m is a positive integer greater than or equal to 2,
j represents the number of bridging groups R 3 which are bound to one backbone of the crosslinked polymer, j being greater than or equal to 1,
k represents the number of backbones of the crosslinked polymer which are bound to one bridging group R 3 , k being greater than or equal to 2,
d′, e′, f′, and y′ are positive numbers,
n is a positive integer greater than 1,
—K 1 is a monovalent radical selected from the group consisting of —NH 2 — and —NH(R 4 )—,
—R 4 is a monovalent radical comprising 1 to 50 carbons,
—R 6 — is a divalent radical selected from the group consisting of a ethylene, 2-propylene, butylene, and combinations thereof,
—Z 1 is a monovalent radical selected from the group consisting of —H, —R 7 , -L 1 -NH 2 , -L 1 -NHR 7 , -L 1 -N(R 7 ) 2 , and hydrogen salt forms of any of the foregoing amine groups,
—R 7 is a monovalent radical comprising 1 to 20 carbons,
-L 1 - is a divalent radical comprising 1 to 20 carbons,
—R 9 is a zwitterionic monovalent radical comprising i) a cationic group selected from the group consisting of quaternary amines, sulfonium groups, phosphonium groups, and combinations thereof, and ii) an anionic group selected from the group consisting of carboxylate (—CO 2 − ), sulphonate (—SO 3 − ), and sulfinate (—SO 2 − ), wherein —R 9 — has a net zero charge,
-D′-Q 1 - is a divalent linking group selected from the group consisting of amides, sulfonamides, sulfinamides, and functional groups having a phosphorous-nitrogen bond,
-Q 1 - is a divalent radical selected from the group consisting of —N(H)— and —N(R 4 )—,
—R 4 is a monovalent radical comprising 1 to 50 carbons, and
-D′- is a divalent radical independently selected from the group consisting of —C(═O)—, —S(═O) 2 —, and —S(═O)—, and groups comprising a phosphorous bonded to a nitrogen of -Q 1 -.

15. The composite membrane of claim 14 , wherein —R 9 comprises a quaternary amine group and a sulfonate group (—SO 3 − ).

16. The composite membrane of claim 14 , wherein —R 9 comprises a quaternary amine group and a carboxylate group (—CO 2 − ).

17. The composite membrane of claim 14 , wherein —R 9 comprises a phosphonium group and a carboxylate group (—CO 2 − ).

18. The composite membrane of claim 14 , wherein m=2 and R 3 -[D′] m is an i

Assignees

• Globalfoundries Inc

Inventors

• Na Young-Hye
• Nelson Alshakim
• Sooriyakumaran Ratnam
• Vora Ankit

Classifications

• B01D2325/48

  Antimicrobial properties · CPC title

• B01D71/56 Primary

  Polyamides, e.g. polyester-amides · CPC title

• B01D71/68 Primary

  Polysulfones; Polyethersulfones · CPC title

• B01D69/125

  In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction · CPC title

• B01D71/40

  Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters · CPC title