Adsorbent comprising metal oxide/hydroxide particles reacted with one or more phosphorous-containing materials having selected organic radicals attached thereto

Claim 2

A process for chemically bonding a monomolecular layer of phosphorous-containing organic material to metal oxide/hydroxide particles to form an active material suitable for use as an adsorbent and having good chemical stability over a pH range of from 1 to 14 which comprises: (a) providing a liquid containing an organic material therein having 1-2 phosphorous-containing groups thereon selected from the class consisting of: (i) phosphonic acid having the formula RPO(OH) 2 ; and (ii) phosphinic acid having the formula RR'PO(OH); where R comprises a 1-30 carbon-containing group and R' comprises hydrogen or a 1-30 carbon-containing group; and (b) contacting the metal oxide/hydroxide particles with said liquid to chemically bond said phosphorous-containing organic material to all of the exposed hydroxyl groups on the surface of said metal oxide/hydroxide particles to form a monomolecular layer of said organic material thereon forming said active material.

Claim 3

The process of claim 1 wherein 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.

Claim 4

The process of claim 1 wherein 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.

Claim 5

The process of claim 3 wherein 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.

Claim 6

The process of claim 1 wherein 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 7

A process for chemically bonding a monomolecular layer of phosphorous-containing organic material to metal oxide/hydroxide particles to form an active material suitable for use as an adsorbent and having good chemical stability over a pH range of from 1 to 14 which comprises: (a) providing a liquid containing an organic material therein having 1-2 phosphorous-containing groups thereon selected from the class consisting of: (i) phosphonic acid having the formula RPO(OH) 2 ; and (ii) phosphinic acid having the formula RR'PO(OH); where R comprises a 1-30 carbon-containing group and R' comprises hydrogen or a 1-30 carbon-containing group; (b) maintaining said liquid containing said phosphorous-containing organic material at a concentration of at least about 0.0001 to 0.1 molar; and (c) contacting the metal oxide/hydroxide particles with said liquid at a temperature of from about 25°-90° C. for a period of from at least 0.1 to about 20 hours to chemically bond said phosphorous-containing organic material to all of the exposed hydroxyl groups on the surface of said metal oxide/hydroxide particles to form a monomolecular layer of said organic material thereon comprising said active material; whereby said surface of said metal oxide/hydroxide particles is substantially free of unreacted hydroxyl groups after said chemical bonding, said active material is stable at a pH of from 1-14, and said active material is insoluble in aqueous media.

Claim 8

A process for chemically bonding a monomolecular layer of phosphorous-containing organic material to metal oxide/hydroxide particles to form an active material suitable for use as an adsorbent and having good chemical stability over a pH range of from 1 to 14 which comprises: (a) providing a liquid containing an organic material therein having 1-2 phosphorous-containing groups thereon selected from the class consisting of: (i) phosphonic acid having the formula RPO(OH) 2 ; and (ii) phosphinic acid having the formula RR'PO(OH); where R comprises a 1-30 carbon-containing group and R' comprises hydrogen or a 1-30 carbon-containing group; (b) maintaining said liquid containing said phosphorous-containing organic material at a concentration of at least about 0.0001 to 0.1 molar; and (c) contacting the metal oxide/hydroxide particles with said liquid at a temperature of from about 25°-90° C. for a period of from at least 0.1 to about 20 hours to chemically bond said phosphorous-containing organic material to all of the exposed hydroxyl groups on the surface of said metal oxide/hydroxide particles to form a monomolecular layer of said organic material thereon comprising said active material; whereby said surface of said metal oxide/hydroxide particles is substantially free of unreacted hydroxyl groups after said chemical bonding, said active material is stable at a pH of from 1-14, and said active material is insoluble in aqueous media.

Claim 9

The process of forming said active material of claim 6 wherein said metal oxide/hydroxide particles have a particle size range of from 50 Angstroms up to 12 millimeters.

Claim 10

The process of forming said active material of claim 7 wherein said particle size range of said metal oxide/hydroxide particles is from about 1 to about 200 microns.

Claim 11

The process of forming said active material of claim 6 wherein said metal oxide/hydroxide particles comprise porous particles having an average pore size of from about 20 Angstroms to about 10 microns in diameter.

Claim 12

The process of forming said active material of claim 9 wherein said porous metal oxide/hydroxide particles have a pore volume of from about 0.1 to about 1.5 ml/gram.

Claim 13

The process of forming said active material of claim 10 wherein said porous metal oxide/hydroxide particles have a surface area of from about 0.10 to about 1000 m 2 /gram.

Claim 14

The process of forming said active material of claim 6 wherein said metal oxide/hydroxide particles comprise an oxide/hydroxide of an element capable of forming an oxide/hydroxide selected from the class consisting of group IB, group IIA, group IIB, group IIIA, IVA, VA, group IIIB, group IVA, group IVB, group VB, group VIB, group VIIB, and group VIII metals; lanthanide series; silicon, boron, selenium, arsenic and tellurium.

Claim 15

The process of forming said active material of claim 12 wherein said metal oxide/hydroxide particles comprise an oxide/hydroxide of a metal selected from the class consisting of aluminum, magnesium, titanium, zirconium, iron, silicon, chromium, zinc, vanadium, and combinations of these metals.

Claim 16

The process of forming said active material of claim 12 wherein said metal oxide/hydroxide particles are selected from the class consisting of alumina, iron oxide, silica, zeolitic materials, zirconia, zinc oxide, magnesia, apatites, and hydrotalcites.

Claim 17

The process of forming said active material of claim 14 wherein said metal oxide/hydroxide particles comprise alumina.

Claim 18

The process of forming said active material of claim 15 wherein said alumina comprises activated alumina having a surface area in the range of 0.1 to 600 m 2 /g.

Claim 19

The process of forming said active material of claim 15 wherein said alumina has a particle size in the range of 50 Angstroms to 12 mm.

Claim 20

The process of forming said active material of claim 6 wherein the thickness of said substantially 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.

Claim 21

The process of forming said active material of claim 6 wherein the thickness of said monomolecular layer of phosphorous-containing organic material chemically bonded to said metal oxide/hydroxide particles is in the range of 20 to 500 Angstroms.

Claim 22

The process of forming said active material of claim 6 wherein said R group of said organic molecule contains at least 5 carbon atoms.

Claim 23

The process of forming said active material of claim 6 wherein said monomolecular layer constitutes 0.01 to 90 wt.% of said active material comprising said phosphorous-containing organic material chemically bonded to said metal oxide/hydroxide particles.

Claim 24

The process of forming said active material of claim 6 wherein said monomolecular layer constitutes about 4 to 50 wt.% of said active material comprising said phosphorous-containing organic material chemically bonded to said metal oxide/hydroxide particles.

Claim 25

The process of forming said active material of claim 20 comprising the further step of treating said reactive material, comprising said metal oxide/hydroxide particles having chemically bonded thereto said phosphorous-containing organic material containing at least 5 carbon atoms, with a second liquid having a phosphorous-containing organic material therein selected from the class consisting of; (a) phosphonic acid having the formula RPO(OH) 2 ; and (b) phosphinic acid having the formula RR'PO(OH); where R comprises a 1-5 carbon group and R' comprises hydrogen or a 1-5 carbon group; said further treatment step acting to react said phosphorous-containing organic material in said second liquid with any remaining surface hydroxyl groups on the surface of said metal oxide/hydroxide particle not reacted in said first treatment.

Claim 26

An active material comprising a metal oxide/hydroxide particle having chemically bonded to reactive sites on a surface thereof, a monomolecular layer of a phosphorous-containing organic material suitable for use as an adsorbent and selected from the class consisting of phosphonic acid having the formula RPO(OH) 2 and phosphinic acid having the formula RR'PO(OH) where R comprises a 1-30 carbon-containing group and R' comprises hydrogen or a 1-30 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 27

An active material comprising a metal oxide/hydroxide particle having chemically bonded to reactive sites on a surface thereof, a monomolecular layer of a phosphorous-containing organic material suitable for use as an adsorbent and selected from the class consisting of phosphonic acid having the formula RPO(OH) 2 and phosphinic acid having the formula RR'PO(OH) where R comprises a 1-30 carbon-containing group and R' comprises hydrogen or a 1-30 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 28

The active material of claim 24 wherein said metal oxide/hydroxide comprises particles having a particle size range of from 50 Angstroms up to 12 millimeters.

Claim 29

The active material of claim 25 wherein said particle size range of said metal oxide/hydroxide particles is from about 1 to about 200 microns.

Claim 30

The active material of claim 25 wherein said metal oxide/hydroxide particles comprise porous particles having an average pore size of from about 1 to about 200 microns in diameter.

Claim 31

The active material of claim 27 wherein said porous metal oxide/hydroxide particles have a pore volume of from about 0.1 to about 1.5 ml/gram.

Claim 32

The active material of claim 27 wherein said porous metal oxide/hydroxide particles have a surface area of from about 0.10 to about 1000 m 2 /gram.

Claim 33

The active material of claim 25 wherein said metal oxide/hydroxide particles comprise an oxide/hydroxide of an element capable of forming an oxide/hydroxide selected from the class consisting of group IB, group IIA, group IIB, group IIIA, IVA, VA, group IIIB, group IVB, group VB, group VIB, group VIIB, and group VIII metals; lanthanide series; silicon, thorium, boron, uranium, selenium, arsenic and tellurium.

Claim 34

The active material of claim 30 wherein said metal oxide/hydroxide particles comprises an oxide/hydroxide of a metal selected from the class consisting of aluminum, magnesium, titanium, zirconium, iron, silicon, chromium, zinc, vanadium, and combinations of these metals.

Claim 35

The active material of claim 30 wherein said metal oxide/hydroxide particles are selected from the class consisting of alumina, iron oxide, silica, zeolitic materials, zirconia, zinc oxide, magensia, apatites, and hydrotalcites.

Claim 36

The active material of claim 32 wherein said metal oxide/hydroxide particles comprise alumina.

Claim 37

The active material of claim 33 wherein said alumina comprises activated alumina having a surface area in the range of 0.1 to 600 m 2 /g.

Claim 38

The active material of claim 33 wherein said alumina has a particle size in the range of 50 Angstroms to 12 millimeters.

Claim 39

The active material of claim 25 wherein 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.

Claim 40

The active material of claim 36 wherein the thickness of said monomolecular layer of phosphorous-containing organic material chemically bonded to said metal oxide/hydroxide particles is in the range of 20 to 500 Angstroms.

Claim 41

The active material of claim 25 wherein said R group of said phosphorous-containing organic molecule contains at least 5 carbon atoms.

Claim 42

The active material of claim 24 wherein either said R group or said R' group may comprise an organic radical selected from the class consisting of long and short chain aliphatic hydrocarbons, aromatic hydrocarbons, carboxylic acids, aldehydes, ketones, amines, amides, thioamides, imides, lactams, anilines, pyridines, piperidines, carbohydrates, esters, lactones, ethers, alkenes, alkynes, alcohols, nitriles, oximes, organosilicones, ureas, thioureas, perfluoro organic molecules, perchloro organic molecules, perbromo organic molecules and combinations of these groups.

Claim 43

The active material of claim 39 wherein either said R group or said R' group may have a functional group attached to a portion of said molecule spaced from said phosphorous-containing group on said molecule selected from the class consisting of a carboxyl group, a glucose group, 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 halogen group, nitrate group, phosphate group, phosphinate group, phosphinite group, phosphonate group, quaternary ammonium salt group and combinations of these groups.

Claim 44

The active material of claim 39 wherein either said R group or said R' 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 --HSO 3 , --N(CH 3 ) 3 Cl, --COONa, --NH 2 and --CN.

Claim 45

The active material of claim 25 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 46

The active material of claim 25 wherein said monomolecular layer constitutes 0.01 to 90 wt.% of said reactive material comprising said phosphorous-containing organic material chemically bonded to said metal oxide/hydroxide particles.

Claim 47

The active material of claim 43 wherein said monomolecular layer constitutes about 4 to 50 wt.% of said reactive material comprising said phosphorous-containing organic material chemically bonded to said metal oxide/hydroxide particles.

Claim 48

An active material suitable for use as an adsorbent and capable of reacting with, attracting, coupling to, or bonding with other atoms, ions, and/or molecules comprising: (a) metal oxide/hydroxide particles consisting essentially of an oxide/hydroxide of an element capable of forming an oxide/hydroxide selected from the class consisting of group IB, group IIA, group IIB, group IIIA, IVA, VA, group IIIB, group IVA, group IVB, group VB, group VIB, group VIIB, and group VIII elements; lanthanide series; selenium, silicon, boron, arsenic, thorium, uranium and tellurium; and (b) chemically bonded to reactive sites on a surface of said metal oxide/hydroxide particles, a monomolecular layer of a phosphorous-containing organic material comprised of a phosphorous-containing group and a carbon-containing group and selected from the class consisting of phosphonic acid having the formula RPO(OH) and phosphinic acid having the formula RR'PO(OH) wherer R comprises a 1-30 carbon-containing group and R 1 comprises hydrogen or a 1-30 carbon-containing group; said bond being formed by reaction of said phosphorous-containing group with said metal oxide/hydroxide particle surface, said carbon-containing group being oriented away from said metal oxide/hydroxide particle surface.

Claim 49

An active material suitable for use as an adsorbent and capable of reacting with, attracting, coupling to, or bonding with other atoms, ions, and/or molecules comprising: (a) metal oxide/hydroxide particles consisting essentially of an oxide/hydroxide of an element capable of forming an oxide/hydroxide selected from the class consisting of group IB, group IIA, group IIB, group IIIA, IVA, VA, group IIIB, group IVA, group IVB, group VB, group VIB, group VIIB, and group VIII elements; lanthanide series; selenium, silicon, boron, arsenic, thorium, uranium and tellurium; and (b) chemically bonded to reactive sites on a surface of said metal oxide/hydroxide particles, a monomolecular layer of a phosphorous-containing organic material comprised of a phosphorous-containing group and a carbon-containing group and selected from the class consisting of phosphonic acid having the formula RPO(OH) and phosphinic acid having the formula RR'PO(OH) wherer R comprises a 1-30 carbon-containing group and R 1 comprises hydrogen or a 1-30 carbon-containing group; said bond being formed by reaction of said phosphorous-containing group with said metal oxide/hydroxide particle surface, said carbon-containing group being oriented away from said metal oxide/hydroxide particle surface.

Claim 50

The active material of claim 45 wherein said R group on said phosphorous-containing organic material comprises a monomer and said R' group, when present, is hydrogen or a monomer.

Claim 51

The active material of claim 45 wherein said R group of said phosphorous-containing organic material is an oligomer containing 2-4 monomers and having a molecular weight of less than 2000.

Claim 52

A process for chemically bonding a monomolecular layer of phosphorous-containing organic material to a metal oxide/hydroxide particle to form an active material suitable for use as an adsorbent and having good chemical stability over a pH range of from 1 to 14 which comprises: (a) providing a liquid containing an organic material therein having 1-2 phosphorous-containing groups thereon selected from the class consisting of: (i) phosphonic acid having the formula RPO(OH) 2 ; and (ii) phosphinic acid having the formula RR'PO(OH); where R comprises a 1-30 carbon-containing group and R' comprises hydrogen or a 1-30 carbon-containing group; and (b) treating the metal oxide/hydroxide particle with said liquid to form said active material by chemically bonding said phosphorous-containing organic material to substantially all of the exposed hydroxyl groups on the surface of said metal oxide/hydroxide particle to form a monomolecular layer of said organic material thereon wherein said phosphonic or phosphinic acid molecules are bonded to said metal oxide/hydroxide particle to form said monomolecular layer; whereby the surface chemistry of said metal oxide/hydroxide particle is changed by the reaction of substantially all of the hydroxy groups on the surface with said phosphorous-containing organic material to form said monomolecular layer to render the resultant active material stable at a pH of from 1-14 and insoluble in aqueous media.

Claim 53

A process for chemically bonding a monomolecular layer of phosphorous-containing organic material to a metal oxide/hydroxide particle to form an active material suitable for use as an adsorbent and having good chemical stability over a pH range of from 1 to 14 which comprises: (a) providing a liquid containing an organic material therein having 1-2 phosphorous-containing groups thereon selected from the class consisting of: (i) phosphonic acid having the formula RPO(OH) 2 ; and (ii) phosphinic acid having the formula RR'PO(OH); where R comprises a 1-30 carbon-containing group and R' comprises hydrogen or a 1-30 carbon-containing group; and (b) treating the metal oxide/hydroxide particle with said liquid to form said active material by chemically bonding said phosphorous-containing organic material to substantially all of the exposed hydroxyl groups on the surface of said metal oxide/hydroxide particle to form a monomolecular layer of said organic material thereon wherein said phosphonic or phosphinic acid molecules are bonded to said metal oxide/hydroxide particle to form said monomolecular layer; whereby the surface chemistry of said metal oxide/hydroxide particle is changed by the reaction of substantially all of the hydroxy groups on the surface with said phosphorous-containing organic material to form said monomolecular layer to render the resultant active material stable at a pH of from 1-14 and insoluble in aqueous media.

Claim 54

The process of claim 48 wherein said step of treating said metal oxide/hydroxide particle with said liquid to form said active material by chemically bonding said phosphorous-containing organic material to substantially all of the exposed hydroxyl groups on the surface of said metal oxide/hydroxide particle to form a monomolecular layer of said organic material thereon further comprises the step of treating said metal oxide/hydroxide particle with a phosphorous-containing organic material comprising a monomer or oligimer having 5 to 30 carbon atoms followed by a second treatment with a phosphorous-containing organic material comprising a monomer or oligimer having less than 6 carbon atoms so that substantially all of the reactive sites on said metal oxide/hydroxide particle are capped or blocked.

Claim 55

The process of claim 49 including the further step of treating the reacted material with a material selected from the class consisting of an organic solvent, an acid, a base, and a combination thereof capable of removing weakly adsorbed molecules on the reacted material to assure formation of the desired monomolecular layer of phosphorous-containing organic material over said metal oxide/hydroxide particle.

Claim 56

The process for forming an active material suitable for use as an adsorbent of claim 48 wherein 90% of said phosphonic or phosphinic acid molecules are bonded to said metal oxide/hydroxide particle to form said monomolecular layer.

Claim 57

The process for forming an active material suitable for use as an adsorbent of claim 48 wherein 98% of said phosphonic or phosphinic acid molecules are bonded to said metal oxide/hydroxide particle to form said monomolecular layer.