Porous materials for solid phase extraction and chromatography and processes for preparation and use thereof

Abstract

Embodiments of the present invention are directed to porous materials for use in solid phase extractions and chromatography. The materials feature at least one hydrophobic component, at least one hydrophilic component and at least one ion-exchange functional group. The materials exhibit superior wetting and ion-exchange performance.

1 . A porous material comprising a copolymer of at least one hydrophobic monomer and at least one hydrophilic monomer, wherein said copolymer further comprises at least one ion-exchange functional moiety selected from the group consisting of an acyclic secondary amine exclusive of polyethylenimine, a cyclic tertiary amine, a substituted acyclic amine, and a substituted cyclic amine. 
     
     
         2 . The porous material of  claim 1 , wherein the porous material comprises a porous particle that comprises said copolymer. 
     
     
         3 . The porous material of  claim 2 , wherein said copolymer is non-sulfonated. 
     
     
         4 . The porous material of  claim 2 , wherein said substituted acyclic amine or said substituted cyclic amine is substituted by an electron withdrawing group. 
     
     
         5 . The porous material of  claim 2  wherein said hydrophobic monomer is divinylbenzene or styrene. 
     
     
         6 . The porous material of  claim 2  wherein said hydrophilic monomer is N-vinylpyrrolidone or N-vinyl acetamide. 
     
     
         7 . The porous material of  claim 2  wherein said copolymer is a poly(divinylbenzene-co-N-vinylpyrrolidone). 
     
     
         8 . The porous material of  claim 2  wherein the hydrophobic monomer is substituted by at least one haloalkyl group, and the ion-exchange functional moiety is formed by reaction of the haloalkyl group with an appropriate starting amine to form an amine selected from the group consisting of an acyclic secondary amine, a cyclic tertiary amine, a substituted acyclic amine, and a substituted cyclic amine. 
     
     
         9 . The porous material of  claim 8 , wherein said haloalkyl is fluoromethyl, chloromethyl, bromomethyl or iodomethyl. 
     
     
         10 . The porous material of  claim 8 , wherein the appropriate starting amine is a primary amine selected from the group consisting of methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, iso-butylamine, tert-butylamine, pentylamine, 1,1-dimethylpropylamine, 1,2-dimethylpropylamine, 1-ethylpropylamine, 2-methylbutylamine, isopentylamine, hexylamine, 1,3-dimethylbutylamine, 3,3-dimethylamine, heptylamine, 2-aminoheptane, octylamine, 1,5-dimethylhexylamine, 2-ethylhexylamine, 1-methylheptylamine, tert-octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine, azirane, azetane, azolane, azinane, azepane, azocane, azonane, azecane, diazatene, diazolane, diazinane, N-methyldiazinane, diazepane, diazocane, diazonane, diazecane, oxazetane, oxazolane, oxazinane, oxazepane, oxazocane, oxazonane, oxazecane, thiazetane, thiazolane, thiazinane, thiazepane, thiazocane, thiazonane, thiazecane, imidazole, benzylamine, N-methylbenzylamine, N-ethylbenzylamine, N-propylbenzylamine, N-butylbenzylamine, N-pentylbenzylamine, N-hexylbenzylamine, N-heptylbenzylamine, N-octylbenzylamine, N-nonylbenzylamine, N-decylbenzylamine, N-undecylbenzylamine, N-dodecylbenzylamine, N-tridecylbenzylamine, N-tetradecylbenzylamine, N-pentadecylbenzylamine, N-hexadecylbenzylamine, N-heptadecylbenzylamine, N-octadecylbenzylamine, dibenzylamine, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N-pentylaniline, N-hexylaniline, N-heptylaniline, N-octylaniline, N-nonylaniline, N-decylaniline, N-undecylaniline, N-dodecylaniline, N-tridecylaniline, N-tetradecylaniline, N-pentadecylaniline, N-hexadecylaniline, N-heptadecylaniline, N-octadecylaniline, bis(2,2,2-trifluoromethyl)amine, phenethylamine, N-methylphenethylamine, 4-methylphenethylamine, 3-phenylpropylamine, 1-methyl-3-phenylpropylamine, N-isopropylbenzylamine, and 4-phenylbutylamine. 
     
     
         11 .- 27 . (canceled) 
     
     
         28 . The porous material of  claim 1 , wherein the porous material comprises a monolith that comprises said copolymer. 
     
     
         29 . (canceled) 
     
     
         30 . A porous material comprising a copolymer having the formula I:
   -(-A-) n -(-B—) n —(—C—) p —  (I)
   and salts thereof,   wherein the order of repeat units A, B and C may be random, block, or a combination of random and block;   wherein   
       
         
           
             
               
                 1 
                 100 
               
               < 
               
                 
                   ( 
                   
                     p 
                     + 
                     n 
                   
                   ) 
                 
                 m 
               
               < 
               
                 100 
                 1 
               
             
           
         
         
           
             and 
           
         
         
           
             
               
                 1 
                 500 
               
               < 
               
                 p 
                 n 
               
               < 
               
                 100 
                 1 
               
             
           
         
         wherein A is selected from the group consisting of 
       
       
         
           
           
               
               
           
         
         wherein B is selected from the group consisting of 
       
       
         
           
           
               
               
           
         
         wherein C is modified A, wherein modified A is selected from the group consisting of 
       
       
         
           
           
               
               
           
         
         and 
         wherein X is —CR 1 R 2 NR 3 R 4  wherein: 
         R 1  and R 2  are the same or different and each is hydrogen or C 1 -C 6  alkyl; 
         R 3  and R 4  are the same or different and each is hydrogen, an electron withdrawing group, C 1 -C 20  alkyl, C 1 -C 20  alkyl substituted by an electron withdrawing group, or R 3  and R 4  taken together form a carbocyclic ring or a heterocyclic ring, wherein the carbocyclic ring or heterocyclic ring can be substituted by an electron withdrawing group, provided that (i) R 1 , R 2 , R 3  and R 4  are not all hydrogen; (ii) if R 1  and R 2  are hydrogen, then R 3  and R 4  are not both unsubstituted C 1 -C 20  alky; and (iii) if R 1  and R 2  are hydrogen, and either of R 3  and R 4  is hydrogen, then the other of R 3  and R 4  is not polyethylenimine. 
       
     
     
         31 .- 49 . (canceled) 
     
     
         50 . The porous material of  claim 30 , wherein the copolymer is 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         51 .- 54 . (canceled) 
     
     
         55 . A porous material comprising a copolymer selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         56 . The porous material of  claim 55 , wherein the porous material comprises a porous particle that comprises said copolymer. 
     
     
         57 . The porous material of  claim 55 , wherein the porous material comprises a monolith that comprises said copolymer. 
     
     
         58 . A solid phase extraction or chromatography material comprising the porous material of  claim 1 . 
     
     
         59 .- 71 . (canceled)