Porous inorganic/organic homogenous copolymeric hybrid materials for chromatographic separation and process for the preparation thereof

Abstract

Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific procedures described herein. Such equivalents were considered to be within the scope of this invention and are covered by the following claims. The contents of all references, issued patents, and published patent applications cited throughout this application are hereby incorporated by reference.

1 . A porous inorganic/organic homogenous copolymeric hybrid material, wherein said material has at least about 10% carbon content by mass.  
     
     
         2 . A porous inorganic/organic homogenous copolymeric hybrid material, wherein said material consists essentially of spherical particles.  
     
     
         3 . The material according to  claim 1 , comprising porous inorganic/organic homogenous copolymeric hybrid particles.  
     
     
         4 . The material according to  claim 1 , wherein said material has from about 15% to about 90% carbon content by mass.  
     
     
         5 - 9 . (canceled)  
     
     
         10 . The material according to  claim 2 , wherein said particles are approximately spherical.  
     
     
         11 . The material according the  claim 10 , wherein said particles have an average diameter of about 0.1 μm to about 60 μm.  
     
     
         12 . (canceled)  
     
     
         13 . The material according to  claim 1 , wherein said material has a specific surface area of about 50-800 m 2 /g.  
     
     
         14 - 17 . (canceled)  
     
     
         18 . The material according to  claim 1 , wherein said material has an average pore diameter of about 20 to 300 Å.  
     
     
         19 . (canceled)  
     
     
         20 . (canceled)  
     
     
         21 . The material according to  claim 1 , wherein said material is hydrolytically stable at a pH of about 1 to about 13.  
     
     
         22 - 25 . (canceled)  
     
     
         26 . The material according to  claim 1 , wherein said material is surface modified by formation of a chemical bond between an inorganic or organic group of the material and a surface modifier.  
     
     
         27 . The material according to  claim 3 , wherein said particles are surface modified by formation of a chemical bond between an inorganic or organic group of the particles and a surface modifier.  
     
     
         28 . The material according to  claim 26  or  27 , wherein the surface modifier is selected from the group consisting of an organic group surface modifier, a silanol group surface modifier, a polymeric coating surface modifier, and combinations thereof.  
     
     
         29 . The material according to  claim 1 , wherein said material is surface modified by a surface modifier selected from the group consisting of an organic group surface modifier, a silanol group surface modifier, a polymeric coating surface modifier, and combinations thereof.  
     
     
         30 . The material according to  claim 26 ,  27 , or  29 , wherein said surface modifier has the formula Z a (R′) b Si—R, where Z═Cl, Br, I, C 1 -C 5  alkoxy, dialkylamino or trifluoromethanesulfonate; a and b are each an integer from 0 to 3 provided that a+b=3; R′ is a C 1 -C 6  straight, cyclic or branched alkyl group, and R is a functionalizing group.  
     
     
         31 . The material according to  claim 26 ,  27 , or  29 , wherein said surface modifier is a polymer coating.  
     
     
         32 . The material according to  claim 31 , wherein said polymer is Sylgard®.  
     
     
         33 . The material according to  claim 30 , wherein R′ is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, isopentyl, hexyl and cyclohexyl.  
     
     
         34 . The material according to  claim 30 , wherein the functionalizing group R is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cyano, amino, diol, nitro, ester, a cation or anion exchange group, and an alkyl or aryl group containing an embedded polar functionality.  
     
     
         35 . The material according to  claim 34 , wherein said functionalizing group R is a C 1 -C 30  alkyl group.  
     
     
         36 . The material according to  claim 34 , wherein said functionalizing group R is a C 1 -C 20  alkyl group.  
     
     
         37 . The material according to  claim 26 ,  27 , or  29 , wherein said surface modifier is selected from the group consisting of octyltrichlorosilane, octadecyltrichlorosilane, octyidimethylchlorosilane, and octadecyldimethylchlorosilane.  
     
     
         38 . The material according to  claim 37 , wherein said surface modifier is octyltrichlorosilane or octadecyltrichlorosilane.  
     
     
         39 . The material according to  claim 26 ,  27  or  29 , wherein said surface modifier is a combination of an organic group surface modifier and a silanol group surface modifier.  
     
     
         40 . The material according to  claim 26 ,  27 , or  29 , wherein said surface modifier is a combination of an organic group surface modifier and a polymeric coating surface modifier.  
     
     
         41 . The material according to  claim 26 ,  27 , or  29 , wherein said surface modifier is a combination of a silanol group surface modifier and a polymeric coating surface modifier.  
     
     
         42 . The material according to  claim 26 ,  27 , or  29 , wherein said surface modifier is a combination of an organic group surface modifier, a silanol group surface modifier, and a polymeric coating surface modifier.  
     
     
         43 . The material according to  claim 26 ,  27 , or  29 , wherein said surface modifier is a silanol group surface modifier.  
     
     
         44 . A porous inorganic/organic homogenous copolymeric hybrid monolith material.  
     
     
         45 . The material according to  claim 44 , comprising coalesced porous inorganic/organic homogenous copolymeric hybrid particles.  
     
     
         46 . The material according to  claim 44  or  45 , wherein said material has at least about 10% carbon content by mass.  
     
     
         47 . The material according to  claim 44  or  45 , wherein said material has from about 15% to about 90% carbon content by mass.  
     
     
         48 - 51 . (canceled)  
     
     
         52 . The material according to  claim 44  or  45 , wherein said inorganic portion of said hybrid monolith material is selected from the group consisting of alumina, silica, titanium oxide, zirconium oxide, ceramic materials, and combinations thereof.  
     
     
         53 . The material according to  claim 44  or  45 , wherein said inorganic portion of said hybrid monolith material is silica.  
     
     
         54 . The material according to  claim 44  or  45 , wherein said surface of said material has been surface modified by a surface modifier selected from the group consisting of an organic group surface modifier, a silanol group surface modifier, a polymeric coating surface modifier, and combinations thereof.  
     
     
         55 . The material according to  claim 54 , wherein the particles have been surface modified with a surface modifier having the formula Z a (R′) b Si—R, where Z═Cl, Br, I, C 1 -C 5  alkoxy, dialkylamino or trifluoromethanesulfonate; a and b are each an integer from 0 to 3 provided that a+b=3; R′ is a C 1 -C 6  straight, cyclic or branched alkyl group, and R is a functionalizing group.  
     
     
         56 . A porous inorganic/organic homogenous copolymeric hybrid material of the formula:  
         (A) x (B) y (C) z    
       wherein the order of repeat units A, B, and C may be random, block, or a combination of random and block; 
 A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond;  
 B is an organosiloxane repeat unit which is bonded to one or more repeat units B or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond;  
 C is an inorganic repeat unit which is bonded to one or more repeat units B or C via an inorganic bond; and  
 x,y are positive numbers and z is a non negative number, wherein when z=0, then 0.002≦x/y≦210, and when z≠0, then 0.0003≦y/z≦500 and 0.002≦x/(y+z)≦210.  
 
     
     
         57 . A porous inorganic/organic homogenous copolymeric hybrid material of the formula:  
         (A) x (B) y (B*) y *(C) z    
       wherein the order of repeat units A, B, B*, and C may be random, block, or a combination of random and block; 
 A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond;  
 B is an organosiloxane repeat units which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond;  
 B* is an organosiloxane repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond, wherein B* is an organosiloxane repeat unit that does not have reactive (i.e., polymerizable) organic components and may further have a protected functional group that may be deprotected after polymerization;  
 C is an inorganic repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic bond; and  
 x,y are positive numbers and z is a non negative number, wherein when z=0, then 0.002≦x/(y+y*)≦210, and when z≠0, then 0.0003≦(y+y*)/z≦500 and 0.002≦x/(y+y*+z)≦210.  
 
     
     
         58 - 65 . (canceled)  
     
     
         66 . A porous inorganic/organic homogenous copolymeric hybrid material of the formula:  
       
         
           
           
               
               
           
         
       
       wherein 
 R 1  is H, F, Cl, Br, I, lower alkyl (e.g., CH 3  or CH 2 CH 3 );  
 R 2  and R 3  are each independently H, F, Cl, Br, I, alkane, substituted alkane, alkene, substituted alkene, aryl, substituted aryl, cyano, ether, substituted ether, embedded polar group;  
 R 4  and R 5  are each independently H, F, Cl, Br, I, alkane, substituted alkane, alkene, substituted alkene, aryl, substituted aryl, ether, substituted ether, cyano, amino, substituted amino, diol, nitro, sulfonic acid, cation or anion exchange groups,  
 0≦a≦2×, 0≦b≦4, and 0≦c≦4, provided that b+c≦4 when a=1; 1≦d≦20,  
 0.0003≦y/z≦500 and 0.002≦x/(y+z)≦210.  
 
     
     
         67 - 70 . (canceled)  
     
     
         71 . A separations device comprising a material according to any of claims  1 ,  2 ,  44 ,  56 , and  57 .  
     
     
         72 . The separations device according to  claim 71 , wherein said device is selected from the group consisting of chromatographic columns, thin layer plates, filtration membranes, sample cleanup devices, and microtiter plates.  
     
     
         73 - 75 . (canceled)  
     
     
         76 . A method of preparing a porous inorganic/organic homogenous copolymeric hybrid material, comprising the steps of 
 (a) hydrolytically condensing an alkenyl-functionalized organosilane with a tetraalkoxysilane,    (b) copolymerizing the product of step (a) with an organic olefin monomer, and    (c) further hydrolytically condensing the product of step (b) to thereby prepare a porous inorganic/organic homogenous copolymeric hybrid material.    
     
     
         77 . (canceled)  
     
     
         78 . A method of preparing a porous inorganic/organic homogenous copolymeric hybrid material, comprising the steps of 
 (a) copolymerizing an organic olefin monomer with an alkenyl-functionalized organosilane, and    (b) hydrolytically condensing the product of step (a) with a tetraalkoxysilane in the presence of a non-optically active porogen to thereby prepare a porous inorganic/organic homogenous copolymeric hybrid material.    
     
     
         79 . A method of preparing a porous inorganic/organic homogenous copolymeric hybrid material, comprising substantially simultaneously copolymerizing an organic monomer with an alkenyl-functionalized organosilane and hydrolytically condensing said alkenyl-functionalized organosilane with a tetraalkoxysilane to thereby prepare a porous inorganic/organic homogenous copolymeric hybrid material.  
     
     
         80 - 121 . (canceled)  
     
     
         122 . The porous inorganic/organic homogenous copolymeric hybrid material of  claim 56 , wherein z=0 and the hybrid material is of the formula:  
         (A) x (B) y    wherein the order of repeat units A and B may be random, block, or a combination of random and block;    A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond;    B is an organosiloxane repeat unit which may or may not be bonded to one or more repeat units B via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond; and 0.002≦x/y≦210.    
     
     
         123 . The porous inorganic/organic homogenous copolymeric hybrid material of  claim 57 , wherein z=0 and the hybrid material is of the formula:  
         (A) x (B) y (B*) y *  wherein the order of repeat units A, B, and B* may be random, block, or a combination of random and block;    A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond;    B is an organosiloxane repeat unit which may or may not be bonded to one or more repeat units B or B* via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond    B* is an organosiloxane repeat unit that does not have reactive (i.e., polymerizable) organic components and may further have a protected functional group that may be deprotected after polymerization ; and 0.002≦x/(y+y*)≦210.    
     
     
         124 - 140 . (canceled)