Novel crosslinked polymeric substrates methods of preparation and end use applications of the substrates

Abstract

A composition of matter wherein the composition comprises a siliceous substrate having silanols on the surface and a polymer selected from the group consisting essentially of a water soluble polymer, a water soluble copolymer, an alcohol soluble polymer, an alcohol soluble copolymer, and combinations of such polymers, wherein the polymer is chemically bonded to the siliceous substrate by a silane linking material having the general formula O 3/2 SiQY that is derived from an alkoxy-functional silane having the general formula (RO) 3 SiQX and processes for preparing the crosslinked polymer that is chemically bonded to the surface of the siliceous substrate.

1 .- 33 . (canceled) 
     
     
         34 . A process for preparing a crosslinked polymer that is chemically bonded to the surface of a siliceous substrate, said process consisting essentially of:
 (I) heating a predetermined amount of alcohol in a reaction vessel with stirring, wherein the alcohol has from 1 to 9 carbon atoms;   (II) adding a predetermined amount of a hydrolysis catalyst selected from organic acids having from 1 to 7 carbon atoms:   (III) adding a predetermined amount of a silanol condensation catalyst;   (IV) adding a predetermined amount of siliceous substrate containing reactive silanols;   (V) adding a predetermined amount of silane coupling agent, said silane being an alkoxy-functional silane having the general formula
   (RO) 3 SiQX 
 wherein R is a hydrocarbon group having from 1 to 6 carbon atoms, Q is a hydrocarbon group having from 0 to 6 carbon atoms, X is a functional group selected from the group consisting of epoxy, halogen, methacrylate, vinyl, amine, allyl, phosphonate, styrlamine, and sulfide; 
   (VI) adding a predetermined amount of polymer, said polymer being selected from the group consisting of
 (i) a water soluble polymer, 
 (ii) a water soluble copolymer, 
 (iii) an alcohol soluble polymer, 
 (iv) an alcohol soluble copolymer, and 
 (v) combinations of (i) to (iv), 
   (VII) stirring the combination of (I) to (VI) for a period of time of 12 hours or less at a temperature of 75° C. or less; wherein the ratio of polymer to siliceous substrate is in the range of P:S wherein P is 0.1 to 50 and S is 99.9 to 50, wherein the incipient silane is present in the amount of 0.1 to 25 weight percent based on the weight of siliceous substrate and wherein the incipient silane is present in an excess with regard to the total amount of reactive silanol groups on the siliceous substrate.   
     
     
         35 . A process as claimed in  claim 34  wherein the weight of the polymer on the siliceous substrate is in the range of about 1 to 20 weight percent based on the total weight of the polymer and the siliceous substrate. 
     
     
         36 . A process as claimed in  claim 34  wherein the weight of the polymer on the siliceous substrate is in the range of about 5 to 15 weight percent based on the total weight of the polymer and the siliceous substrate. 
     
     
         37 . A process as claimed in  claim 34  wherein the weight of the polymer on the siliceous substrate is in the range of about 7 to 12 weight percent based on the total weight of the polymer and the siliceous substrate. 
     
     
         38 . A process as claimed in  claim 34  wherein the alcohol is ethanol. 
     
     
         39 . A process as claimed in  claim 34  wherein the alcohol is propanol. 
     
     
         40 . A process as claimed in  claim 34  wherein the alcohol is isopropanol. 
     
     
         41 . A process as claimed in  claim 34  wherein the alcohol is a mixture of alcohols. 
     
     
         42 . A process as claimed in  claim 34  wherein the organic acid is acetic acid. 
     
     
         43 . A process as claimed in  claim 34  wherein the amount of organic acid present in the reaction vessel provides a pH of 4.5 or less. 
     
     
         44 . A process as claimed in  claim 34  wherein the condensation catalyst is a water soluble alkylbenzylsulfonic acid. 
     
     
         45 . A process as claimed in  claim 44  wherein the condensation catalyst is toluene sulfonic acid. 
     
     
         46 . A process as claimed in  claim 34  wherein the condensation catalyst is an alkyl titanate. 
     
     
         47 . A process as claimed in  claim 46  wherein the condensation catalyst is isopropyl titanate. 
     
     
         48 . A process as claimed in  claim 46  wherein the condensation catalyst is ethyl titanate. 
     
     
         49 . A process as claimed in  claim 46  wherein the condensation catalyst is butyl titanate. 
     
     
         50 . A process as claimed in  claim 46  wherein the condensation catalyst is n-propyl titanate. 
     
     
         51 . A process as claimed in  claim 34  wherein the condensation catalyst is present in the reaction vessel is 0.05 to 5.0 weight percent based on the weight of the siliceous substrate. 
     
     
         52 . A process as claimed in  claim 34  wherein the process time does not exceed twelve hours. 
     
     
         53 . A process as claimed in  claim 34  wherein the silane linking material is derived
 from the silane 
 
       
         
           
           
               
               
           
         
       
       wherein  n  has a value of 1 to 3. 
     
     
         54 . A process as claimed in  claim 34  wherein the surface area of the siliceous substrate is about 3 to 300 m 2 /gram. 
     
     
         55 . A process as claimed in  claim 34  wherein the polymer is polyethylene imine. 
     
     
         56 . A process as claimed in  claim 34  wherein the polymer is an acrylic polymer. 
     
     
         57 . A process as claimed in  claim 34  wherein the polymer is a polyol polymer. 
     
     
         58 . A process as claimed in  claim 34  wherein the polymer is a polyamine polymer. 
     
     
         59 . A process as claimed in  claim 34  wherein the polymer has a molecular weight in the range of 1000 to 200,000 Daltons. 
     
     
         60 . A process for preparing a cross linked polymer that is chemically bonded to the surface of a siliceous substrate, said process consisting essentially of:
 (I) heating a predetermined amount of alcohol and water in a reaction vessel with stirring, wherein the alcohol has from 1 to 9 carbon atoms and wherein the ratio of alcohol to water is in the range of 99 to 1:1 to 99;   (II) adding a predetermined amount of a hydrolysis catalyst selected from organic acids having from 1 to 7 carbon atoms:   (III) adding a predetermined amount of a silanol condensation catalyst;   (IV) adding a predetermined amount of precipitated siliceous substrate having silanols on the surface;   (V) adding a predetermined amount of silane coupling agent, said silane being an alkoxy-functional silane having the general formula
   (RO) 2 SiQX 
 wherein R is a hydrocarbon group having from 1 to 6 carbon atoms, Q is a hydrocarbon group having from 0 to 6 carbon atoms, X is a residue from a functional group selected from the group consisting of epoxy, halogen, methacrylate, vinyl, amine, allyl, phosphonate, styrlamine, and sulfide; 
   (VI) adding a predetermined amount of polymer, said polymer being selected from the group consisting of
 (i) a water soluble polymer, 
 (ii) a water soluble copolymer, 
 (iii) an alcohol soluble polymer, 
 (iv) an alcohol soluble copolymer, and 
 (v) combinations of (i) to (iv), 
   (VIII) stirring the combination of (I) to (VI) for a period of time of 15 hours or less at a temperature of 75° C. or less; wherein the ratio of polymer to siliceous substrate is in the range of P:S wherein P is 0.1 to 50 and S is 99.9 to 50, wherein the incipient silane is present in the amount of 0.1 to 25 weight percent based on the weight of siliceous substrate and wherein the incipient silane is present in an excess with regard to the total amount of reactive silanol groups on the siliceous substrate.   
     
     
         61 . A process as claimed in  claim 60  wherein the organic acid is acetic acid. 
     
     
         62 . A process as claimed in  claim 60  wherein the amount of organic acid present in the reaction vessel provides a pH of 4.5 or less. 
     
     
         63 . A process as claimed in  claim 60  wherein the condensation catalyst is a water soluble alkylbenzylsulfonic acid. 
     
     
         64 . A process as claimed in  claim 63  wherein the condensation catalyst is toluene sulfonic acid. 
     
     
         65 . A process as claimed in  claim 63  wherein the condensation catalyst is an alkyl titanate. 
     
     
         66 . A process as claimed in  claim 65  wherein the condensation catalyst is isopropyl titanate. 
     
     
         67 . A process as claimed in  claim 65  wherein the condensation catalyst is ethyl titanate. 
     
     
         68 . A process as claimed in  claim 65  wherein the condensation catalyst is butyl titanate. 
     
     
         69 . A process as claimed in  claim 65  wherein the condensation catalyst is n-propyl titanate. 
     
     
         70 . A process as claimed in  claim 60  wherein the condensation catalyst present in the reaction vessel is 0.05 to 5.0 weight percent based on the weight of the siliceous substrate. 
     
     
         71 . A process as claimed in  claim 60  wherein the process time does not exceed twelve hours. 
     
     
         72 . A process as claimed in  claim 60  wherein the silane linking material is derived
 from the silane 
 
       
         
           
           
               
               
           
         
       
       wherein  n  has a value of 1 to 3. 
     
     
         73 . A process as claimed in  claim 60  wherein the surface area of the siliceous substrate is about 3 to 300 m 2 /gram. 
     
     
         74 . A process as claimed in  claim 60  wherein the polymer is polyethyleneimine. 
     
     
         75 . A process as claimed in  claim 60  wherein the polymer is an acrylic polymer. 
     
     
         76 . A process as claimed in  claim 60  wherein the polymer is a polyol polymer. 
     
     
         77 . A process as claimed in  claim 60  wherein the polymer is a polyamine polymer. 
     
     
         78 . A process as claimed in  claim 60  wherein the polymer has a molecular weight in the range of 1000 to 200,000 Daltons. 
     
     
         79 . A process as claimed in  claim 60  wherein the weight of the polymer on the siliceous substrate is in the range of about 1 to 20 weight percent based on the total weight of the polymer and the siliceous substrate. 
     
     
         80 . A process as claimed in  claim 60  wherein the weight of the polymer on the siliceous substrate is in the range of about 5 to 30 weight percent based on the total weight of the polymer and the siliceous substrate. 
     
     
         81 . A process as claimed in  claim 60  wherein the weight of the polymer on the siliceous substrate is in the range of about 7 to 15 weight percent based on the total weight of the polymer and the siliceous substrate. 
     
     
         82 . A process for preparing a crosslinked polymer that is chemically bonded to the surface of a siliceous substrate, said process consisting essentially of:
 (I) heating a predetermined amount of water in a reaction vessel with stirring;   (II) adding a predetermined amount of a siliceous substrate having reactive silanols;   (III) thereafter, adding a predetermined amount of incipient silane to provide a silane linking material, said silane being an alkoxy-functional silane having the general formula
   (RO) 3 SiQX 
 wherein R is a hydrocarbon group having from 1 to 6 carbon atoms, Q is a hydrocarbon group having from 0 to 6 carbon atoms, X is a functional group selected from the group consisting of epoxy, halogen, methacrylate, vinyl, amine, allyl, phosphonate, styrlamine, and sulfide; 
   (IV) thereafter, adding a predetermined amount of silanol condensation catalyst;   (V) thereafter, adding a predetermined amount of polymer, said polymer being selected from the group consisting of
 (i) a water soluble polymer, 
 (ii) a water soluble copolymer, 
 (iii) an alcohol soluble polymer, 
 (iv) an alcohol soluble copolymer, and 
 (v) combinations of (i) to (iv), 
   (VI) thereafter, stirring the combination of (1) to V for a period of time of 15 hours or less at a temperature of 100° C. or less; wherein the incipient silane is present in the amount of 0.1 to 25 weight percent based on the amount of siliceous substrate and wherein the incipient silane is present in an excess with regard to the total amount of reactive silanol groups of the siliceous substrate.   
     
     
         83 . A process for preparing a crosslinked polymer that is chemically bonded to the surface of a siliceous substrate, said process consisting essentially of:
 (I) heating a predetermined amount of alcohol in a reaction vessel with stirring, wherein the alcohol has from 1 to 9 carbon atoms;   (II) adding a predetermined amount of a silanol condensation catalyst;   (III) adding a predetermined amount of siliceous substrate containing reactive silanols;   (VI) adding a predetermined amount of silane coupling agent, said silane coupling agent being an alkoxy-functional silane having the general formula
   (RO) 3 SiQX 
 wherein H is a hydrocarbon group having from 1 to 6 carbon atoms, Q is a hydrocarbon group having from 0 to 6 carbon atoms, X is a functional group selected from the group consisting of epoxy, halogen, methacrylate, vinyl, amine, allyl, phosphonate, styrlamine, and sulfide; 
   (V) adding a predetermined amount of polymer, said polymer being selected from the group consisting of
 (i) a water soluble polymer, 
 (ii) a water soluble copolymer, 
 (iii) an alcohol soluble polymer, 
 (iv) an alcohol soluble copolymer, and 
 (v) combinations of (I) to (iv), 
   (VI) stirring the combination of (I) to (VI) for a period of time of 12 hours or less at a temperature of 75° C. or less; wherein the ratio of polymer to siliceous substrate is in the range of P:S wherein P is 0.1 to 50 and S is 99.9 to 50, wherein the incipient silane is present in the amount of 0.1 to 25 weight percent based on the weight of siliceous substrate and wherein the incipient silane is present in an excess with regard to the total amount of reactive silanol groups on the siliceous substrate.   
     
     
         84 . A process for preparing a cross linked polymer that is chemically bonded to the surface of a siliceous substrate, said process consisting essentially of:
 (I) heating a predetermined amount of alcohol and water in a reaction vessel with stirring, wherein the alcohol has from 1 to 9 carbon atoms and wherein the ratio of alcohol to water is in the range of 99 to 1:1 to 99;   (II) adding a predetermined amount of a silanol condensation catalyst;   (III) adding a predetermined amount of precipitated siliceous substrate having silanols on the surface;   (IV) adding a predetermined amount of silane coupling agent, said silane coupling agent being an alkoxy-functional silane having the general formula
   (RO) 3 SiQX 
 wherein R is a hydrocarbon group having from 1 to 6 carbon atoms, Q is a hydrocarbon group having from 0 to 6 carbon atoms, X is a residue from a functional group selected from the group consisting of epoxy, halogen, methacrylate, vinyl, amine, allyl, phosphonate, styrlamine, and sulfide; 
   (V) adding a predetermined amount of polymer, said polymer being selected from the group consisting of
 (i) a water soluble polymer, 
 (ii) a water soluble copolymer, 
 (iii) an alcohol soluble polymer, 
 (iv) an alcohol soluble copolymer, and 
 (v) combinations of (1) to (iv), 
   (VII) stirring the combination of (I) to (VI) for a period of time of 15 hours or less at a temperature of 75° C. or less; wherein the ratio of polymer to siliceous substrate is in the range of P:S wherein P is 0.1 to 50 and S is 99.9 to 50, wherein the incipient silane is present in the amount of 0.1 to 25 weight percent based on the weight of siliceous substrate and wherein the incipient silane is present in an excess with regard to the total amount of reactive silanol groups on the siliceous substrate.   
     
     
         85 . A method of process stream purification, the method comprising treating a process stream effluent using a composition obtained by the process as claimed n  claim 151 . 
     
     
         86 . A method of process stream purification as claimed in  claim 85  wherein metal ions are removed from the process stream. 
     
     
         87 . (canceled) 
     
     
         88 . A method of cleaning a waste stream, the method comprising treating a waste stream using a composition obtained by the process as claimed in  claim 151 . 
     
     
         89 . A method of cleaning a waste stream as claimed in  claim 88  wherein metal ions are removed from the waste stream. 
     
     
         90 . (canceled) 
     
     
         91 . A method of recovering resources, the method comprising treating a fluid containing said recoverable resources with a composition obtained from the process as claimed in  claim 151 . 
     
     
         92 .- 93 . (canceled) 
     
     
         94 . The method as claimed in  claim 91  wherein the fluid is water and the recoverable resource is any of the metals or a combination of any of the metals selected from the group consisting of metals selected from:
 i. silver, ii. gold, iii. cadmium, iv. chromium, v. copper vi. hafnium, vii. iridium, viii. manganese, ix. molybdenum, x. niobium, xi. osmium, xii. palladium, xiii. platinum, xiv. rhenium, xv. rhodium, xvi. ruthenium, xvii tantalum, xviii. technetium, xix. titanium, xx. tungsten, xxi. zinc, xxii. zirconium and, heavy metals selected from the group consisting of a. barium, b. bismuth, c. cerium, d. lead, e. antimony, f. tin, g. thallium, h. uranium, j. strontium, k. lead, l. iron, m. aluminum, n. plutonium, o. radium, and p. aluminum zirconium complexes. 
 
     
     
         95 .- 146 . (canceled) 
     
     
         147 . A method of removing dyes from waste water processing, the method comprising contacting the waste water containing the dyes with a composition obtained from the process as claimed in  claim 151  and thereafter separating the composition from the waste water. 
     
     
         148 - 149 . (canceled) 
     
     
         150 . A method of binding and prevention of free dye transfer in a washing process wherein a composition obtained by the process as claimed in  claim 151  is added to a washing process to prevent the transfer of dye to fabrics, clothes or films. 
     
     
         151 . A process for preparing a crosslinked polymer that is chemically bonded to the surface of a siliceous substrate, said process consisting essentially of:
 (I) heating a predetermined amount of water in a reaction vessel with stirring;   (II) adding a predetermined amount of hydrolysis catalyst that is an organic acid, said organic acid having from 1 to 7 carbon atoms:   (III) thereafter, adding a predetermined amount of a siliceous substrate having reactive silanols;   (IV) thereafter, adding a predetermined amount of incipient silane to provide a silane linking material, said silane being an alkoxy-functional silane having the general formula
   (RO) 3 SiQX 
 wherein R is a hydrocarbon group having from 1 to 6 carbon atoms, 0 is a hydrocarbon group having from 0 to 6 carbon atoms, X is a functional group selected from the group consisting of epoxy, halogen, methaorylate, vinyl, amine, allyl, phosphonate, styrlamine, and sulfide; 
   (V) thereafter, adding a predetermined amount of silanol condensation catalyst selected from alkyl titanates;   (VI) thereafter, adding a predetermined amount of polymer, said polymer being selected from the group consisting of
 (i) a water soluble polymer, 
 (ii) a water soluble copolymer, 
 (iii) an alcohol soluble polymer, 
 (iv) an alcohol soluble copolymer, and 
 (v) combinations of (i) to (iv), 
   (VII) thereafter, additionally stirring the combination of the components of (I) to (VI) for a period of time of 15 hours or less at a temperature of 100° C. or less; wherein the incipient silane is present in the amount of 0.1 to 25 weight percent based on the amount of siliceous substrate and wherein the incipient silane is present in an excess with regard to the total amount of reactive silanol groups of the siliceous substrate.   
     
     
         152 . A process as claimed in  claim 151  wherein the condensation catalyst is isopropyl titanate. 
     
     
         153 . A process as claimed in  claim 151  wherein the condensation catalyst is ethyl titanate. 
     
     
         154 . A process as claimed in  claim 151  wherein the condensation catalyst is butyl titanate. 
     
     
         155 . A process as claimed in  claim 151  wherein the condensation catalyst is n-propyl titanate. 
     
     
         156 . A process as claimed in  claim 151  wherein the condensation catalyst is present in the reaction vessel is 0.05 to 5.0 weight percent based on the weight of the siliceous substrate. 
     
     
         157 . A process as claimed in  claim 151  wherein the process time does not exceed twelve hours. 
     
     
         158 . A process as claimed in  claim 151  wherein the silane linking material is derived from the silane 
       
         
           
           
               
               
           
         
       
       wherein  n  has a value of 1 to 3. 
     
     
         159 . A process as claimed in  claim 151  wherein the surface area of the siliceous substrate is about 3 to 300 m 2 /gram. 
     
     
         160 . A process as claimed in  claim 151  wherein the polymer is polyethylene imine. 
     
     
         161 . A process as claimed in  claim 151  wherein the polymer is an acrylic polymer. 
     
     
         162 . A process as claimed in  claim 151  wherein the polymer is a polyol polymer. 
     
     
         163 . A process as claimed in  claim 151  wherein the polymer is a polyamine polymer. 
     
     
         164 . A process as claimed in  claim 151  wherein the polymer has a molecular weight in the range of 1000 to 200,000 Daltons. 
     
     
         165 . A process as claimed in  claim 151  wherein the weight of the polymer on the siliceous substrate is in the range of about 1 to 20 weight percent based on the total weight of the polymer and the siliceous substrate. 
     
     
         166 . A process as claimed in  claim 151  wherein the weight of the polymer on the siliceous substrate is in the range of about 5 to 15 weight percent based on the total weight of the polymer and the siliceous substrate. 
     
     
         167 . A process as claimed in  claim 151  wherein the weight of the polymer on the siliceous substrate is in the range of about 7 to 12 weight percent based on the total weight of the polymer and the siliceous substrate.