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

Patent metadata

Field	Value
Publication number	US-9708199-B2
Application number	US-201213628679-A
Country	US
Kind code	B2
Filing date	Sep 27, 2012
Priority date	Sep 28, 2011
Publication date	Jul 18, 2017
Grant date	Jul 18, 2017

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

The invention claimed is:

1. A surface-modified material for removing oil from water comprising a substrate having a plurality of embedded silica or metal oxide nanostructures; wherein the nanostructures are covalently bonded to a polymer through a quaternized amine such that the surface of the surface-modified material is oleophilic and/or hydrophobic at a first condition and oleophobic and/or hydrophilic at a second condition, and wherein the polymer comprises a block copolymer with (a) at least one wettability-responsive block and (b) at least one hydrophobic and oleophilic block, wherein the wettability responsive block is polypyrrole, poly(2-vinylpyridine), or poly(4-vinylpyridine), wherein the substrate has a different chemical composition than the polymer.

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

3. The surface-modified material of claim 1 , wherein the surface-modified material is oleophilic in air at a first condition and oleophobic in air at a second condition.

4. 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.

5. The surface-modified material of claim 1 , wherein the nanostructures comprise nanoparticles, nanowires, nanorods, nanobelts, nanotubes, layered nanostructures, or a combination thereof.

6. The surface-modified material of claim 5 , wherein the nanostructures have an average size from around 1 nm to 10 μm.

7. The surface-modified material of claim 1 , 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).

8. The surface-modified material of claim 1 , wherein the at least one hydrophobic block is a hydrophobic homogenous polymer.

9. The surface-modified material of claim 8 , 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).

10. 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, or nanostructures.

11. The surface-modified material of claim 10 , wherein the textile, membrane, paper, metal mesh, metal foam or polymer foam has an average pore size in the range from 10 nm to 5,000 μm.

12. The surface-modified material of claim 1 , wherein the substrate comprises a nonporous solid.

13. The surface-modified material of claim 10 , wherein the substrate comprises the textile, membrane, or polymer foam, wherein the textile, membrane, or polymer foam 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), polydimethylsiloxane, poly(phenyl methyl siloxane), poly(4-dimethylsilyl styrene), poly(4-methyl styrene), poly(isobutylene), poly(N-isopropylacrylamide), polyacrylamide, polyaniline, poly(acrylic acid), poly(methylacrylic acid), poly(2-(diethylamino)ethylmethacrylate, 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.

14. The surface-modified material of claim 10 , wherein the substrate comprises the metal mesh or metal foam, wherein the metal mesh or metal foam 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.

15. The surface-modified material of claim 14 , wherein the metal mesh or metal foam comprises metal, 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.

16. The surface-modified material of claim 12 , wherein the 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), polydimethylsiloxane, poly(phenyl methyl siloxane), poly(-dimethylsilyl styrene), poly(4-methyl styrene), poly(isobutylene), poly(N-isopropylacrylamide), polyacrylamide, polyaniline, poly(acrylic acid), poly(methylacrylic acid), poly(2-(diethylamino)ethylmethacrylate, 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.

17. The surface-modified material of claim 1 , wherein the polymer was bonded to the substrate through a grafting to and/or grafting from process.

18. The surface-modified material of claim 17 , wherein the grafting from process comprises atom transfer radical polymerization or reversible addition-fragmentation chain transfer polymerization.

19. The surface-modified material of claim 17 , wherein the grafting to process comprises functionalized polymer molecules reacting with complementary functional groups located on the substrate surface to form tethered chains.

20. The surface-modified material of claim 19 , wherein the functional groups of the functionalized polymer molecules comprise amino groups, pyridyl groups, carboxy groups, and/or hydroxy groups.

21. The surface-modified material of claim 19 , wherein the complementary functional groups located on the substrate surface comprise epoxy groups, amino groups, carboxy groups, hydroxy groups, and/or haloalkyl groups.

22. The surface-modified material of claim 19 , wherein the complementary functional groups are introduced on the substrate surface by a silanization reaction between a silane and the substrate.

23. The surface-modified material of claim 22 , wherein the silane comprises an

Assignees

• Zhang Lianbin
• Wang Peng
• Univ King Abdullah Sci & Tech

Inventors

• Zhang Lianbin
• Wang Peng

Classifications

• C01P2006/16

  Pore diameter · CPC title

• B01D2325/38

  Hydrophobic membranes · CPC title

• B01D69/02 Primary

  characterised by their properties · CPC title

• C01P2004/17

  Nanostrips, nanoribbons or nanobelts, i.e. solid nanofibres with two significantly differing dimensions between 1-100 nanometer · CPC title

• Y10T428/31612

  As silicone, silane or siloxane · CPC title