Method of making ionic liquid mediated sol-gel sorbents

Patent metadata

Field	Value
Publication number	US-9555394-B2
Application number	US-201314046302-A
Country	US
Kind code	B2
Filing date	Oct 4, 2013
Priority date	May 21, 2009
Publication date	Jan 31, 2017
Grant date	Jan 31, 2017

Abstract

Ionic liquid (IL)-mediated sol-gel hybrid organic-inorganic materials present enormous potential for effective use in analytical microextraction. One obstacle to materializing this prospect arises from high viscosity of ILs significantly slowing down sol-gel reactions. A method was developed which provides phosphonium-based, pyridinium-based, and imidazolium-based IL-mediated advanced sol-gel organic-inorganic hybrid materials for capillary microextraction. Scanning electron microscopy results demonstrate that ILs can serve as porogenic agents in sol-gel reactions. IL-mediated sol-gel coatings prepared with silanol-terminated polymers provided up to 28 times higher extractions compared to analogous sol-gel coatings prepared without any IL in the sol solution. This study shows that IL-generated porous morphology alone is not enough to provide effective extraction media: careful choice of the organic polymer and the precursor with close sol-gel reactivity must be made to ensure effective chemical bonding of the organic polymer to the created sol-gel material to be able to provide the desired sorbent characteristics.

First claim

What is claimed is:

1. A method for making an extraction column, comprising the steps:
making a sol-gel mixture, further comprising:
obtaining a first sol-gel precursor, wherein the first precursor is hydroxy-terminated poly(dimethylsiloxane), bis[(3-methyldimethoxysilyl)-propyl]polypropylene oxide, poly(tetrahydrofuran) 250, poly(ethylene glycol) MW 600, or poly(dimethylsiloxane-co-diphenylsiloxane), dihydroxyterminated;
adding an ionic liquid to the first sol-gel precursor to form a precursor mixture, wherein the ionic liquid is a phosphonium-based ionic liquid, imidazolium-based ionic liquid, pyridinium-based ionic liquid, or a combination thereof;
adding methylene chloride to the precursor mixture;
mixing a second sol-gel precursor into the precursor mixture, wherein the second sol-gel precursor is an alkoxy compound of an element M, where M is silicon, titanium, zirconium, germanium, vanadium, zinc, tantalum, niobium, or tungsten;
mixing a catalyst into the precursor mixture to form a sol-gel mixture, wherein the catalyst is acid, base, or fluoride compound;

adding the sol-gel mixture to the interior lumen of an extraction column;
allowing the sol-gel mixture to bond to the interior wall of the extraction column forming a sol-gel coating; and
removing any unbonded sol-gel mixture from the extraction column.

2. The method of claim 1 , wherein the alkoxy compound is tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, or tetrabutoxysilane.

3. The method of claim 1 , wherein the ionic liquid is trihexyltetradecylphosphonium tetrafluroborate, 1-methyl-3-octylimidazolium chloride, or 4-methyl-N-butylpyridinium tetrafluoroborate.

4. The method of claim 1 , wherein the catalyst is an organic acid or inorganic acid.

5. The method of claim 4 , wherein the catalyst has a pKa of less than 4.

6. The method of claim 1 , wherein the catalyst is trifluoroacetic acid.

7. The method of claim 1 , further comprising adding a deactivating agent to the sol-gel mixture after the second sol-gel precursor has been mixed into the precursor-ionic liquid mixture, wherein the deactivating agent is poly(methylhydrosiloxane).

8. The method of claim 1 , further comprising conditioning the extraction column, comprising the steps of
placing the extraction column in a gas chromatograph oven;
passing helium gas along the exterior surface of the sol-gel coating;
elevating the temperature of the gas chromatograph oven until the oven reaches a conditioning temperature;
where the conditioning temperature is 400° C. or below.

9. The method of claim 8 , wherein the extraction column is further conditioned by bringing the extraction column to room temperature and passing combination methylene chloride/methanol along the exterior surface of the coating.

Assignees

• Malik Abdul
• Shearrow Anne M
• Univ South Florida

Inventors

• Malik Abdul
• Shearrow Anne M

Classifications

• B01J20/291 Primary

  Gel sorbents · CPC title

• B01J20/26

  Synthetic macromolecular compounds · CPC title

• G01N2030/567

  coating · CPC title

• B01J20/3272

  Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds · CPC title

• B01J2220/86

  Sorbents applied to inner surfaces of columns or capillaries · CPC title