Molecularly imprinted polymers (MIPS) for the selective removal of inorganic contaminants from liquids

• US 20070090058A1
• Filed: 09/12/2006
• Published: 04/26/2007
• Est. Priority Date: 09/12/2005
• Status: Active Grant

• Current Assignee: MIP Solutions, Inc.
• Original Assignee: MIP Solutions, Inc.
• Inventors: Southard, Glen
• Granted Patent: US 7,476,316 B2
• Time in Patent Office: Days
• US Class Current: 210/727
• CPC Class Codes: B01D 1/00 Evaporating evaporation in general, e.g. of liquids for gas phase reactions B01B1/005 ; removal of incrustation B08B; preparation of starch C08B30/00; sugar industry C13; prevention of incrustation C23F; drying solid materials or objects by evaporating liquids therefrom F26
• CPC Class Codes: B01J 20/26 Synthetic macromolecular compounds
• CPC Class Codes: B01J 20/268 Polymers created by use of a template, e.g. molecularly imprinted polymers
• CPC Class Codes: C02F 1/285 using synthetic organic sorbents

Abstract

A method of creating a cationic molecularly imprinted polymer bead that can bind inorganic target compounds is disclosed and described. The cationic molecularly imprinted polymer bead can be formed by complexing a target compound with a cationic ligand, polymerizing the cationic ligands to form the bead, and then extracting the target compound from the bead. The cationic ligand complex can have an octanol water partition coefficient of about 1 to about 10. The cationic molecularly imprinted polymer bead can have a porous structure containing a plurality of complexing cavities for selectively bind specific target compounds for removal from potable water, mine effluent, industrial effluent, or other fluids.

Claims

1. A method of preparing a cationic molecularly imprinted polymer bead, comprising the steps of:

a) complexing an cationic ligand with an inorganic target compound to form a target cationic ligand complex, wherein the cationic ligand complex has an octanol water partition coefficient with an absolute value of about 1 to about 10;

b) polymerizing the target cationic ligand complex to form the cationic molecularly imprinted polymer bead; and

c) extracting the target compound from the cationic molecularly imprinted polymer bead.

2. The method of claim 1, wherein the cationic ligand is selected from the group consisting of cationic oxygen containing heterocyclics, cationic nitrogen containing heterocyclics, cationic sulfur containing heterocyclics, cationic phosphorous containing heterocyclics, ammonium salts, phosphonium salts, acylinium salts, metallocenium salts, amidinium salts, imminium salts, trityl salts, and mixtures thereof.

3. The method of claim 1, wherein the cationic ligands is 4-vinylbenzyl-N,N-dimethyl-N-decylammonium, 4-vinylbenzyl-N-decyl-N-methyl-D-glucammonium, N-methyl vinylpyridinium, or 4-vinylbenzyl-N,N-dimethyl-D-glucammonium.

4. The method of claim 1, wherein the target compound is selected from the group consisting of bromide, chloride, cyanide, fluoride, oxyanions of antimony, oxyanions of arsenic, oxyanions of beryllium, oxyanions of bromine, oxyanions of carbon, oxyanions of chlorine, oxyanions of chromium, oxyanions of nitrogen, oxyanions of phosphorous, oxyanions of selenium, oxyanions of sulfur, oxyanions of manganese, oxyanions of technetium, oxyanium of boron, oxyanions of vanadium, molybdenum anions, tungsten anions, and mixtures thereof.

5. The method of claim 4, wherein the target compound is arsenate, arsenite, nitrate, nitrite, cyanide, dicyanoaurate or dicyanoargentate.

6. The method of claim 1, wherein the octanol water partition coefficient has an absolute value from about 1.0 to about 3.0.

7. The method of claim 1, wherein the cationic ligand has a solubility parameter from about 10 to about 20.

8. The method of claim 1, wherein the cationic ligand complex has a redox potential of at least 0.3 eV versus SCE.

9. The method of claim 1, wherein the step of polymerizing is by suspension polymerization.

10. The method of claim 1, wherein the step of polymerizing further comprises cross-linking the cationic molecularly imprinted polymer bead.

11. A cationic molecularly imprinted polymer bead made by the method of claim 1.

12. A method of selectively removing inorganic target compounds from a liquid comprising contacting a liquid that contains at least one target compound with a cationic molecularly imprinted polymer bead, said cationic molecularly imprinted polymer bead having at least one selective binding cavity containing cationic ligands for binding the target compound, and when said binding cavity contains the target compound, a target cationic ligand complex is formed having an octanol water partition coefficient with an absolute value of about 1 to about 10.

13. The method of claim 12, wherein the cationic ligand is selected from the group consisting of cationic oxygen containing heterocyclics, cationic nitrogen containing heterocyclics, cationic sulfur containing heterocyclics, cationic phosphorous containing heterocyclics, ammonium salts, phosphonium salts, acylinium salts, metallocenium salts, amidinium salts, imminium salts, trityl salts, and mixtures thereof.

14. The method of claim 12, wherein the target compound is arsenate, arsenite, nitrate, nitrite, cyanide, dicyanoaurate, or dicyanoargentate.

15. The method of claim 12, wherein the octanol water partition coefficient has an absolute value from about 1.0 to about 3.0.

16. The method of claim 12, wherein the cationic molecularly imprinted polymer bead is cross-linked.

17. A cationic molecularly imprinted polymer bead comprising a porous structure having a plurality of complexing cavities therein, wherein the complexing cavities contain cationic ligands spatially oriented for binding a specific inorganic target compound, and when said bead contains the specific target compound, a target cationic ligand complex is formed having an octanol water partition coefficient with an absolute value of about 1 to about 10.

18. The cationic molecularly imprinted polymer bead of claim 17, wherein the bead contains different complexing cavities for binding different target compounds.

19. The cationic molecularly imprinted polymer bead of claim 17, wherein the cationic ligand is selected from the group consisting of cationic oxygen containing heterocyclics, cationic nitrogen containing heterocyclics, cationic sulfur containing heterocyclics, cationic phosphorous containing heterocyclics, ammonium salts, phosphonium salts, acylinium salts, metallocenium salts, amidinium salts, imminium salts, trityl salts, and mixtures thereof.

20. The cationic molecularly imprinted polymer bead of claim 17, wherein the target compound is arsenate, arsenite, nitrate, nitrite, cyanide, dicyanoaurate, or dicyanoargentate.

21. The cationic molecularly imprinted polymer bead of claim 17, wherein the bead has a diameter of about 50 microns to 1.5 mm.

22. The cationic molecularly imprinted polymer bead of claim 17, wherein the octanol water partition coefficient has an absolute value from about 1.0 to about 3.0.

23. The cationic molecularly imprinted polymer bead of claim 17, wherein the bead is cross-linked.