Method for increasing the fouling resistance of inorganic membranes by grafting with organic moieties

Patent metadata

Field	Value
Publication number	US-10322377-B2
Application number	US-201515120484-A
Country	US
Kind code	B2
Filing date	Feb 24, 2015
Priority date	Feb 24, 2014
Publication date	Jun 18, 2019
Grant date	Jun 18, 2019

Abstract

Provided herein are filtration membranes for water treatment, and methods for preventing fouling of such membranes. The method described herein comprises grafting the membrane surface with an organic moiety, by reacting the surface with an organometallic reagent, a phosphonate, a phosphinate, or an organosilane.

First claim

What is claimed is:

1. An antifouling treatment method of a hydrophilic membrane comprising an oxide and/or hydroxide of silicon or a metal, comprising grafting a surface of the membrane comprising said oxide and/or hydroxide with an organic moiety R 1 or R 10 by contacting said surface with an organometallic reagent, a phosphonate, a phosphinate, or an organosilane to obtain a treated membrane which is at least in part hydrophilic, wherein
R 1 is selected from the group consisting of C 1-12 alkyl, C 6-10 aryl, C 7-16 alkylaryl, C 7-16 arylalkyl, —R 7 [OR 8 ] n R 9 , C 3-8 cycloalkyl, C 3-8 cycloalkenyl, C 4-10 cycloalkylalkyl, C 4-10 cycloalkenylalkyl, C 2-12 alkenyl, 3- to 8-membered heterocyclyl, 5- to 10-membered heteroaryl, heterocyclylC 1-6 alkyl, heteroarylC 1-4 alkyl and C 2-12 alkynyl; wherein R 7 and R 8 are independently from each other C 1-4 alkylene; n is an integer from 1 to 4; and R 9 is C 1-4 alkyl;
and
R 10 is selected from the group consisting of C 1-8 alkylene, C 6-10 arylene, C 7-16 alkylarylene, C 7-16 arylalkylene, —R 11 [OR 12 ] m R 13 —, C 3-8 cycloalkylene, C 3-8 cycloalkenylene, C 4-10 cycloalkylalkylene, C 4-10 cycloalkenylalkylene, C 2-12 alkenylene, 3- to 8-membered heterocyclylene, 5- to 10-membered heteroarylene, heterocyclylC 1-6 alkylene, heteroarylC 1-4 alkylene and C 2-12 alkynylene; wherein R 11 , R 12 , and R 13 are independently from each other C 1-4 alkylene, and m is an integer from 1 to 4;
wherein R 1 and R 10 are optionally substituted with one or more groups independently selected from hydroxyl, —OR 4 , amino, halo, sulfhydryl, —SR 5 , —COOH, and —COOR 6 ; wherein R 4 , R 5 , R 6 are independently selected from C 1-6 alkyl, halo and C 6-10 aryl, and
wherein the treated membrane has a ratio of water permeability compared to a same non-treated membrane of at least 8/20.

2. The method according to claim 1 , wherein said membrane comprises an oxide and/or hydroxide of an element M 1 , and said surface of said membrane is grafted with an organic functional group R 1 , via
a direct M 1 -R 1 bond;
at least one M 1 -O—P—R 1 bond;
a M 1 -O—Si—R 1 bond;
a M 1 -O—P—R 10 —P—O-M 1 bond; or
a M 1 -O—Si—R 10 —Si—O-M 1 bond;
wherein
M 1 is a metal or silicon; and R 1 and R 10 have the same meaning as defined in claim 1 .

3. The method according to claim 1 , wherein said organometallic reagent is a compound of the formula R 1 -M 2 , or of formula R 1 -M 2 -X, or of formula R 1 -M 2 -R 1′ ; wherein
M 2 is Li or Mg, and X is halo;
R 1 has the same meaning as in claim 1 ; and
R 1′ is, the same or different from R 1 , selected from the group consisting of C 1-12 alkyl, C 6-10 aryl, C 7-16 alkylaryl, C 7-16 arylalkyl, —R 7 [OR 8 ] n R 9 , C 3-8 cycloalkyl, C 3-8 cycloalkenyl, C 4-10 cycloalkylalkyl, C 4-10 cycloalkenylalkyl, C 2-12 alkenyl, 3- to 8-membered heterocyclyl, 5- to 10-membered heteroaryl, heterocyclylC 1-6 alkyl, heteroarylC 1-4 alkyl and C 2-12 alkynyl; optionally substituted with one or more groups independently selected from hydroxyl, —OR 4 , amino, halo, sulfhydryl, —SR 5 , —COOH, and —COOR 6 ; wherein
R 4 , R 5 , R 6 are independently selected from C 1-6 alkyl, halo and C 6-10 aryl;
R 7 and R 8 are independently from each other C 1-4 alkylene;
n is an integer from 1 to 4; and
R 9 is C 1-4 alkyl.

4. The method according to claim 1 , wherein said phosphonate or phosphinate is a compound chosen from
formula (I)

or a salt or ester thereof, wherein R 1 has the same meaning as in claim 1 ;
or
formula (III)

or a salt or ester thereof, wherein
R 1 has the same meaning as in claim 1 ; and
R 1′ is, the same or different from R 1 , selected from the group consisting of C 1-12 alkyl, C 6-10 aryl, C 7-16 alkylaryl, C 7-16 arylalkyl, —R 7 [OR 8 ] n R 9 , C 3-8 cycloalkyl, C 3-8 cycloalkenyl, C 4-10 cycloalkylalkyl, C 4-10 cycloalkenylalkyl, C 2-12 alkenyl, 3- to 8-membered heterocyclyl, 5- to 10-membered heteroaryl, heterocyclylC 1-6 alkyl, heteroarylC 1-4 alkyl and C 2-12 alkynyl; optionally substituted with one or more groups independently selected from hydroxyl, —OR 4 , amino, halo, sulfhydryl, —SR 5 , —COOH, and —COOR 6 ; wherein
R 4 , R 5 , R 6 are independently selected from C 1-6 alkyl, halo and C 6-10 aryl;
R 7 and R 8 are independently from each other C 1-4 alkylene;
n is an integer from 1 to 4; and
R 9 is C 1-4 alkyl;
or
formula (IV)

or a salt or ester thereof, wherein R 10 has the same meaning as in claim 1 .

5. The method according to claim 1 , wherein R 1 is C 1-6 alkyl, phenyl, or —R 7 [OR 8 ] n R 9 ; wherein
R 7 and R 8 are independently from each other C 1-4 alkylene;
n is an integer from 1 to 4; and
R 9 is C 1-4 alkyl.

6. The method according to claim 1 , for protecting said membrane against fouling when used for water treatment.

7. The method according to claim 1 , wherein R 1 is C 1-6 alkyl or phenyl; and R 10 is C 1-6 alkylene or phenylene.

8. A method for the purification of an aqueous composition comprising the steps of
(i) providing a functionalized at least in part hydrophilic inorganic matrix comprising an oxide and/or hydroxide of an element M 1 , wherein a surface of said inorganic matrix is grafted with an organic functional group R 1 or R 10 , wherein,
M 1 is a metal or silicon;
R 1 is selected from the group consisting of C 1-12 alkyl, C 6-10 aryl, C 7-16 alkylaryl, C 7-16 arylalkyl, —R 7 [OR 8 ] n R 9 , C 3-8 cycloalkyl, C 3-8 cycloalkenyl, C 4-10 cycloalkylalkyl, C 4-10 cycloalkenylalkyl, C 2-12 alkenyl, 3- to 8-membered heterocyclyl, 5- to 10-membered heteroaryl, heterocyclylC 1-6 alkyl, heteroarylC 1-4 alkyl and C 2-12 alkynyl; wherein R 7 and R 8 are independently from each other C 1-4 alkylene; n is an integer from 1 to 4; and
R 9 is C 1-4 alkyl;
and
R 10 is selected from the group consisting of C 1-8 alkylene, C 6-10 arylene, C 7-6 alkylarylene, C 7-16 arylalkylene, —R 11 [OR 12 ] m R 13 —, C 3-8 cycloalkylene, C 3-8 cycloalkenylene, C 4-10 cycloalkylalkylene, C 4-10 cycloalkenylalkylene, C 2-12 alkenylene, 3- to 8-membered heterocyclylene, 5- to 10-membered heteroarylene, heterocyclylC 1-6 alkylene, heteroarylC 1-4 alkylene and C 2-12 alkynylene; wherein R 11 , R 12 , and R 13 are independently from each other C 1-4 alkylene;
wherein R 1 and R 10 are optionally substituted with one or more groups independently selected from hydroxyl, —OR 4 , amino, halo, sulfhydryl, —SR 5 , —COOH, and —COOR 6 ; wherein R 4 , R 5 , R 6 are independently selected from C 1-6 alkyl, halo and C 6-10 aryl, and m is an integer from 1 to 4; and
wherein the treated membrane has a ratio of water permeability compared to a same non-treated membrane of at least 8/20; and
(ii) filtering said aqueous composition with said functionalized inorganic matrix to obtain a purified aqueous composition.

9. The method according to claim 8 , wherein R 1 or R 10 is grafted on said surface via
a direct M 1 -R 1 bond;
at least one M 1 -O—P—R 1 bond;
a M 1 -O—Si—R 1 bond;
a M 1 -O—P—R 10 —P—O-M 1 bond; or
a M 1 -O—Si—R 10 —Si—O-M 1 bond.

10. The method according to claim 8 , wherein, M 1 is selected from the group consisting of titanium, zirconium, aluminium, silicon, strontium, yttrium, lanthanum, hafnium, thorium, iron, manganese, or combinations the

Assignees

• Vito Nv
• Univ Antwerpen

Inventors

• Buekenhoudt Anita
• Wyns Kenny
• Mustafa Ghulam
• Meynen Vera

Classifications

• C02F1/444

  by ultrafiltration or microfiltration · CPC title

• B01D61/027

  Nanofiltration · CPC title

• C02F1/442

  by nanofiltration · CPC title

• C02F2303/20

  Prevention of biofouling · CPC title

• B01D69/148

  Organic/inorganic mixed matrix membranes · CPC title