Grafted membranes and substrates having surfaces with switchable superoleophilicity and superoleophobicity and applications thereof

Patent metadata

Field	Value
Publication number	US-2017326504-A1
Application number	US-201715613720-A
Country	US
Kind code	A1
Filing date	Jun 5, 2017
Priority date	Sep 28, 2011
Publication date	Nov 16, 2017
Grant date	—

Abstract

Disclosed herein are surface-modified membranes and other surface-modified substrates exhibiting switchable oleophobicity and oleophilicity in aqueous media. These membranes and substrates may be used for variety of applications, including controllable oil/water separation processes, oil spill cleanup, and oil/water purification. Also provided are the making and processing of such surface-modified membranes and other surface-modified substrates.

First claim

1 . A surface-modified material for removing oil from water, comprising:
a polymer grafted to and/or from a substrate such that a surface of a surface-modified material is oleophilic and/or hydrophobic at a first condition and oleophobic and/or hydrophilic at a second condition; wherein the substrate has a different chemical composition than the polymer; wherein the polymer comprises a wettability-responsive polymer, polymer segment, or polymer block comprising poly(N-isopropylacrylamide), polyacrylamide, polypyrrole, polythiophene, polyaniline, poly(2-vinylpyridine), poly(4-vinylpyridine), poly(acrylic acid), poly(methylacrylic acid), poly(2-(diethylamino)ethylmethacrylate, poly(spiropyran methacrylate), poly(methacryloyl ethylene phosphate), poly[2-(methacryloyloxy)ethyl]-dimethyl(3-sulfopropyl)ammonium hydroxide, or poly[2-(methacryloyloxy)-ethyl-trimethylammonium chloride].

2 . The surface-modified material of claim 1 , wherein the grafting from process includes atom transfer radical polymerization or reversible addition-fragmentation chain transfer polymerization.

3 . The surface-modified material of claim 1 , wherein the grafting to process includes functionalized polymer molecules reacting with complementary functional groups located on the substrate surface to form tethered chains.

4 . The surface-modified material of claim 3 , wherein the functional groups of the functionalized polymer molecules include carboxy groups, hydroxy groups, amino groups, and/or pyridyl groups.

5 . The surface-modified material of claim 3 , wherein the complementary functional groups located on the surface of the substrate include epoxy groups, amino groups, carboxy groups, hydroxy groups, and/or haloalkyl groups.

6 . The surface-modified material of claim 3 , wherein the complementary functional groups are introduced on the surface of the substrate by a silanization reaction between a silane and the substrate.

7 . The surface-modified material of claim 6 , wherein the silane includes an epoxy group, amino group, carboxy group, hydroxyl group, and/or haloalkyl group.

8 . The surface-modified material of claim 1 , wherein the surface-modified material is oleophilic in aqueous media and/or air at a first condition and oleophobic in aqueous media and/or air at a second condition.

9 . The surface-modified material of claim 1 , wherein the first and second conditions are selected from the group consisting of a certain temperature, voltage, pH, illuminance, pressure, and a combination thereof.

10 . The surface-modified material of claim 1 , wherein the polymer comprises a block copolymer including at least one wettability-responsive block and at least one hydrophobic and oleophilic block.

11 . The surface-modified material of claim 10 , wherein the wettability-responsive block is poly(N-isopropylacrylamide), polyacrylamide, polypyrrole, polythiophene, polyaniline, poly(2-vinylpyridine), poly(4-vinylpyridine), poly(acrylic acid), poly(methylacrylic acid), poly(2-(diethylamino)ethylmethacrylate, poly(spiropyran methacrylate), poly(methacryloyl ethylene phosphate), poly[2-(methacryloyloxy)ethyl]-dimethyl(3-sulfopropyl)ammonium hydroxide, or poly[2-(methacryloyloxy)-ethyl-trimethylammonium chloride].

12 . The surface-modified material of claim 10 , wherein the hydrophobic block is poly(acrylonitrile), poly(phenyl methyl siloxane), polystyrene, poly(4-dimethylsilyl styrene), poly(4-methyl styrene), poly(dimethyl siloxane), polyethylene, polypropylene, poly(isobutylene), polyamide, or poly(vinylidene fluoride).

13 . The surface-modified material of claim 1 , wherein the polymer comprises a mixed polymer including at least one hydrophobic homogenous polymer and one polymer that is responsive to wettability.

14 . The surface-modified material of claim 13 , wherein the hydrophobic homogenous polymer is poly(acrylonitrile), poly(phenyl methyl siloxane), polystyrene, poly(4-dimethylsilyl styrene), poly(4-methyl styrene), poly(dimethyl siloxane), polyethylene, polypropylene, poly(isobutylene), polyamide, or poly(vinylidene fluoride).

15 . The surface-modified material of claim 13 , wherein the wettability-responsive polymer is poly(N-isopropylacrylamide), polyacrylamide, polypyrrole, polythiophene, polyaniline, poly(2-vinylpyridine), poly(4-vinylpyridine), poly(acrylic acid), poly(methylacrylic acid), poly(2-(diethylamino)ethylmethacrylate, poly(spiropyran methacrylate), poly(methacryloyl ethylene phosphate), poly[2-(methacryloyloxy)ethyl]-dimethyl(3-sulfopropyl)ammonium hydroxide, poly[2-(methacryloyloxy)-ethyl-trimethylammonium chloride], or mixtures thereof.

16 . The surface-modified material of claim 1 , wherein the substrate comprises a textile, a membrane, a polymer foam, a metal mesh, a metal foam, paper, glass, nanostructures, or nonporous solid.

17 . The surface-modified material of claim 16 , wherein the textile, membrane, polymer foam, or nonporous solid comprises cellulose, nylon, polyester, polyethylene terephthalate, polyurethane polylactide, polypropylene, polyethylene, polysulfone, polyamide, polyvinyl chloride, polytetrafluoroethylene, polycarbonate, polyacrylonitrile, polybutylene terephthalate, polyimide, polymethyl methacrylate, polyetheretherketone, polyetherketone, polyetherimide, polyethersulfone, polymethylpentene, polyoxymethylene, polyphthalamide, polyphenylene oxide, polyphenylene sulfide, ethylene propylene rubber, styrene butadiene rubber, ethylene propylene diene monomer rubber, chitosan, alginate, gelatin, poly(N-isopropylacrylamide), poly(4-vinylpyridine), poly(2-vinylpyridine), polydimethylsiloxane, poly(phenyl methyl siloxane), poly(4-dimethylsilyl styrene), poly(4-methyl styrene), poly(isobutylene), poly(N-isopropylacrylamide), polyacrylamide, polypyrrole, polythiophene, polyaniline, poly(acrylic acid), poly(methylacrylic acid), poly(2-(diethylamino)ethylmethacrylate, poly(spiropyran methacrylate), poly(methacryloyl ethylene phosphate), poly[2-(methacryloyloxy)ethyl]-dimethyl(3-sulfopropyl)ammonium hydroxide, poly[2-(methacryloyloxy)-ethyl-trimethylammonium chloride], polyvinylpyrrolidone, or mixtures or blends thereof.

18 . The surface-modified material of claim 16 , wherein the metal mesh, metal foam, or nonporous solid comprises metal, metal oxide of the metal, metal chloride of the metal, metal hydroxide of the metal, alloy of the metals, hybrids of the metal oxides, hybrids of the metal chlorides, or hybrids of the metal hydroxides.

19 . The surface-modified material of claim 18 , wherein the metal comprises at least one of copper, iron, nickel, titanium, zinc, aluminum, silver, gold, palladium, platinum, silicon, vanadium, zirconium, cobalt, lead, chromium, barium, manganese, magnesium, yttrium, hafnium, thallium, indium, tin, arsenic, selenium, tellurium, bismuth, gallium, germanium, cadmium, iridium, tungsten, tantalum, niobium, molybdenum, strontium, calcium, an alloy thereof, an oxide thereof, or a mixture thereof.

20 . The surface-modified material of claim 1 , wherein the polymer comprises a plurality of nitrogen-containing heteroaryl (C3-C12) groups.

Assignees

• Univ King Abdullah Sci & Tech

Inventors

• Zhang Lianbin
• Wang Peng

Classifications

• B01D69/02 Primary

  characterised by their properties · CPC title

• B01D2325/38

  Hydrophobic membranes · CPC title

• C09K3/32

  for absorbing liquids to remove pollution, e.g. oil, gasoline, fat · CPC title

• C09C1/3081

  Treatment with organo-silicon compounds · CPC title

• D06M13/513

  with at least one carbon-silicon bond · CPC title