Active material useful as adsorbent comprising metal oxide/hydroxide particles reacted with one or more phosphorous-containing materials

Claim 2

An active material comprising metal oxide/hydroxide particles having chemically bonded to reactive sites on a surface thereof, a monomolecular layer of a phosphorous-containing organic material comprised of a phosphorous-containing group and a carbon-containing group, said bond being formed by reaction of said phosphorous-containing group with said metal oxide/hydroxide surface, said carbon-containing group being oriented away from said metal oxide/hydroxide surface.

Claim 3

The active material of claim 1 wherein said phosphorous-containing organic material is a phosphonic acid having the formula RPO(OH)₂ or a phosphinic acid having the formula RRʹPO(OH) wherein R comprises a carbon-containing group and Rʹ comprises hydrogen or a carbon-containing group.

Claim 4

The active material of claim 1 wherein said phosphorous-containing organic material is a phosphoric acid having the formual (RO)PO(OH)₂ or a phosphoric acid having the formula (RO)(RʹO)PO(OH) where R comprises a carbon-containing group and Rʹ comprises a carbon-containing group.

Claim 5

The active material of any of claims 1 to 3 wherein said mono-­molecular layer of phosphorous-containing organic material is chemically bonded to at least 25% of the reactive sites on said metal oxide/hydroxide surface.

Claim 6

The active material of any of the preceding claims wherein said metal oxide/hydroxide comprises particles having one or more of the following properties: (a) a particle size range of from 50 Angstroms up to 12 millimeters; (b) the particles comprise porous particles having an average pore size of from about 1 to about 200 microns in diameter; (c) the particles comprise porous particles which have a pore volume of from about 0.1 to about 1.5 ml/grams and/or (d) the particles comprise porous particles which have a surface area of from about 0.10 to about 1000 m²/gram. (e) the thickness of said monomolecular layer of phosphorous-­containing organic material chemically bonded to said metal oxide/hydroxide particles is in the range of 10 to 5,000 Angstroms, or is in the range of 20 to 500 Angstroms.

Claim 7

The active material of any of the preceding claims wherein said metal oxide/hydroxide particles: (1) comprise an oxide/hydroxide of an element capable of forming an oxide/hydroxide from group IB, group IIA, group IIB, group III, IVA, VA, group IIIB, group IVB, group VB, group VIB, group VIIB, or group VIII metals; lanthanide series; silicon, thorium, boron, uranium, selenium, arsenic or tellurium; (2) comprise an oxide/hydroxide of a metal consisting of aluminum, magnesium, titanium, zirconium, iron, silicon, chromium, zinc, vanadium, or combinations of these metals; or (3) consist of alumina, iron oxide, silica, zeolitic materials, zirconia, zinc oxide, magnesia, apatites, or hydrotalcites, said alumina being preferred.

Claim 8

The active material of claim 6 wherein said alumina (a) comprises activated alumina having a surface area in the range of 0.1 to 600 m²/g; and/or (b) has a particle size ian the range of 50 Angstroms to 12 millimeters.

Claim 9

The active material of any of claims 2 to 7 wherein in said formulas R and Rʹ are in accordance with one or more of the following definitions: (a) said R group of said phosphorous-containing organic molecule contains at least 5 carbon atoms; (b) either said R group or said Rʹ group may comprise an organic radical consisting of long and short chain aliphatic hydrocarbons, aromatic hydrocarbons, carboxylic acids, aldehydes, ketones, amines, amides, thioamides, imides, lactams, anilines, pyridines, piperidines, anhydrides, carbohydrates, esters, lactones, ethers, alkenes, alkynes, alcohols, nitriles, oximes, organosilicones, sulfur containing organic compounds, ureas, thioureas, perfluoro, perchloro, perbromo organic molecules or combinations of these groups; (c) either said R group or said Rʹ group may have a functional group attached to a portion of said molecule spaced from said phosphorous-­containing group on said molecule consisting of a carboxyl group, e.g., a carboxymethyl group, a glucose group, a monoclonal antibody, a cyano group, a cyanate group, isocyanate group and thiocyanate group, a phenyl group, a diphenyl group, a tertiary butyl group, a sulfonic group, a benzyl sulfonic group, a protein group such as protein A (staphytococcal protein A), pharmaceutical compounds, yeasts, microbes, whole cells, an enzyme group, a dye group, a chelated metal group, a tag molecule, a halogen group, nitrate group, phosphate group, phosphinate group, phosphinite group, phosphonate group, quaternary ammonium salt group or combinations of these groups; (d) either said R group or said Rʹ group may have a cation exchange functional group attached to a portion of said molecule spaced from said phosphorous-containing group on said molecule and selected from the class consisting of -HSO₃, -N(CH₃)₃Cl, -COONa, -NH₂ and -CN.

Claim 10

The active material of any of the preceding claims wherein said monomolecular layer of organic material having a phosphorous-containing group is substantially free of hydroxyl groups after chemically bonding to said metal oxide/hydroxide particles.

Claim 11

A chromatographic packing material comprising a monomolecular layer of one or more phosphonic acids bonded to a particulate metal oxide/hydroxide support material, preferably wherein said metal oxide/hydroxide comprises aluminum oxide/hydroxide.

Claim 12

A chromatographic packing material comprising a monomolecular layer of one or more phosphonic acids bonded to a particulate metal oxide/hydroxide support material, preferably wherein said metal oxide/hydroxide comprises aluminum oxide/hydroxide.

Claim 13

The chromatographic packing material of claim 10 wherein said particulate metal oxide/hydroxide support material has one or more of the following properties: (a) it has a particle size range of from about 0.5 to about 300 microns. (b) it has a particle size range of from about 1 to about 80 microns. (c) it has a pore diameter range of from about 20 to about 10,000 Angstroms. (d) it has a pore diameter range of from about 40 to about 1000 Angstroms. (e) it has a pore volume of from about 0.1 to about 2 milliliters/gram. (f) it has a pore volume of from about 0.3 to about 1.5 milliliters/gram.

Claim 14

The chromatographic packing material of claim 10 or 11 wherein said metal oxide/hydroxide particle comprises: (1) an oxide/hydroxide of an element capable of forming an oxide/hydroxide consisting of group IB, group IIA, group IIB, group IIIA, group IIIB, group IVA, group IVB, group VA, group VB, group VIB, group VIIB, or group VIII metals; lanthanide series; silicon, thorium, boron, uranium, selenium, arsenic or tellurium; or (2) an oxide/hydroxide of a metal consisting of aluminum, magnesium, titanium, zirconium, iron, silicon, chromium, zinc, vanadium, or combinations of these metals.

Claim 15

The chromatographic packing material of any of claims 10 to 12 wherein said monomolecular layer of said one or more phosphonic acid bonded to said particulate support material comprises a mixture of: (a) from about 2 to about 97% of one or more phosphonic acids having the formula RPO(OH)₂ wherein R is a 5-30 carbon saturated or unsaturated aliphatic hydrocarbon or an aromatic hydrocarbon; and (b) from about 5 to about 75% of one or more phosphonic acids having the formula RʹPO(OH)₂ wherein Rʹ is a 1-4 carbon saturated or unsaturated aliphatic hydrocarbon.

Claim 16

A chromatographic packing material of any of claims 10 to 13 wherein said phosphonic acid having the formula RʹPO(OH)₂ consists essentially of methyl phosphonic acid which is reacted with hydroxl groups on said support material after reaction between said support material and said one or more phosphonic acids having 5-30 carbons thereon in an amount sufficient to react with any remaining reactive hydroxyl sites on said support material.

Claim 17

A process for chemically bonding a monolayer of phosphorous-­containing organic material to metal oxide/hydroxide particles to form an active material which comprises: (a) providing a liquid containing an organic material therein having 1-2 phosphorous-containing groups thereon consisting of (i) phosphonic acid having the formula RPO(OH)₂; (ii) phosphinic acid having the formula RRʹPO(OH); (iii) phosphoric acid monoester having a formula (RO)PO(OH)₂; or (iv) phosphoric acid diester having a formula (RO)(RʹO)PO(OH); where R comprises a carbon-containing group and Rʹ comprises a carbon-containing group; and (b) contacting the metal oxide/hydroxide with said liquid to chemically bond said phosphorous-containing material to at least 25% of the reactive sites on said metal oxide/hydroxide to form a monolayer of said organic material thereon forming said active material.

Claim 18

A process for chemically bonding a monolayer of phosphorous-­containing organic material to metal oxide/hydroxide particles to form an active material which comprises: (a) providing a liquid containing an organic material therein having 1-2 phosphorous-containing groups thereon consisting of (i) phosphonic acid having the formula RPO(OH)₂; (ii) phosphinic acid having the formula RRʹPO(OH); (iii) phosphoric acid monoester having a formula (RO)PO(OH)₂; or (iv) phosphoric acid diester having a formula (RO)(RʹO)PO(OH); where R comprises a carbon-containing group and Rʹ comprises a carbon-containing group; and (b) contacting the metal oxide/hydroxide with said liquid to chemically bond said phosphorous-containing material to at least 25% of the reactive sites on said metal oxide/hydroxide to form a monolayer of said organic material thereon forming said active material.

Claim 19

The process of claim 15 wherein the steps are conducted under one or more of the following conditions: (a) said step of providing a liquid containing an organic material therein having 1-2 phosphorous-containing groups thereon further comprises maintaining a concentration of said phosphorous-containing organic material in said liquid of at least about 0.1 molar; (b) said step of contacting said metal oxide/hydroxide particles with said liquid containing said phosphorous-containing organic material further comprises maintaining said contact for from about 0.1 to about 20 hours; (c) said step of contacting said metal oxide/hydroxide particles with said liquid containing said phosphorous-containing organic material further comprises maintaining said contact for from about 0.5 to about 4 hours; (d) said step of contacting said metal oxide/hydroxide particles with said liquid containing said phosphorous-containing organic material further comprises maintaining the temperature of the reactants at about 5-150°C during said contacting step.

Claim 20

The process of claim 15 or 16 wherein said metal oxide/hydroxide particles and said phosphorous-containing material are as defined in any of claims 5 to 9.

Claim 25

The method of claim 18 or 19 wherein the steps are conducted under one or more of the following conditions: (a) said step of further reacting said particulate support material with one or more phosphonic acids having the formula RʹPO(OH)₂ comprises further reacting said particulate material with methylphosphonic acid; (b) the concentration of said phosphonic acids is from about 0.001 to about 0.1 molar; (c) in each of said steps, said phosphonic acids are reacted with said support material in a non-aqueous media for a period of from about 1 to not more than about 20 hours at a temperature of from about 5°C up to about 200°C to form said monomolecular layer on said metal oxide/hydroxide support material; (d) in each of said steps, said phosphonic acids are reacted with said support material for a period of from about 1 to not more than about 20 hours in an aqueous media at a temperature of from about 25°C up to about 90°C to form said monomolecular layer on said metal oxide/hydroxide support material.