Synthesis of antimicrobial silsesquioxane-silica hybrids

Abstract

One-pot synthetic methods are disclosed for synthesizing curable, antimicrobial silsesquioxane-silica hybrids by hydrolytically co-condensing a tetraalkoxysilane with two different trialkoxysilanes. Particles are also disclosed that are substantially spherical and have an ordered lamellar internal structure. In addition, polymers prepared from the curable, antimicrobial silsesquioxane-silica hybrids and co-monomers are disclosed.

1 - 42 . (canceled) 
     
     
         43 . A plurality of particles, wherein each of said particles comprises:
 a silsesquioxane-silica hybrid;   wherein each of said particles has a substantially spherical morphology; wherein each of said particle has a substantially ordered lamellar internal structure;   wherein each of said particles is mesoporous; and   comprising a reacted residue of a trialkoxysilane of formula III:   
       
         
           
           
               
               
           
         
         wherein 
         R a  is independently a functional group comprising at least one curing group selected from the group consisting of acrylate, methacrylate, (C 2 -C 8 )alkenyl, glycidyloxy, epoxy, sulfonate, carboxylate, ester, amino, acrylamide, methacrylamide, isocyanato, amino acid, nucleic acid, and mercapto(C 1 -C 6 )alkyl; 
         R b  is independently 
       
       
         
           
           
               
               
           
         
         wherein: 
         R c  is (C 1 -C 2 )alkyl; 
         R d  is (C 1 -C 2 )alkyl or phenyl; 
         R e  is (C 6 -C 22 )alkyl; 
         X −  is an anion selected from the group consisting of chloride, bromide, fluoride, iodide, sulfonate, and acetate; and 
         each R Y  is, independently, H, (C 1 -C 8 )alkyl, or trifluoro-substituted (C 1 -C 8 )alkyl, are substantially homogeneously distributed throughout each of said particle; and 
         a reacted residue of a tetraalkoxysilane of formula I: 
       
       
         
           
           
               
               
           
         
         wherein A 1 , A 2 , A 3 , and A 4  are each independently selected from the group consisting of H, C 1 -C 8 alkyl, and trifluoro-substituted (C 1 -C 8 )alkyl, 
         is in a molar ratio of from 1-32 with the trialkoxysilane of formula III, and 
         the reacted residues are substantially homogenously distributed throughout each of said particles. 
       
     
     
         44 . The particles of  claim 43 , wherein A 1 , A 2 , A 3 , and A4 are each ethyl. 
     
     
         45 . The particles of  claim 44 , wherein R c  and R d  are methyl, and R 3  is octadecyl. 
     
     
         46 . A method of preparing a silsesquioxane-silica hybrid particles, comprising:
 hydrolytically co-condensing a tetraalkoxysilane of formula I:   
       
         
           
           
               
               
           
         
         with a trialkoxysilane of formula II: 
       
       
         
           
           
               
               
           
         
         or a trialkoxysilane of formula III: 
       
       
         
           
           
               
               
           
         
         wherein:
 A 1 , A 2 , A 3 , and A 4  are each independently selected from the group consisting of H, C 1 -C 8 alkyl, and trifluoro-substituted (C 1 -C 8 )alkyl; 
 R a  is independently a functional group comprising at least one curing group selected from the group consisting of acrylate, methacrylate, (C 2 -C 8 )alkenyl, glycidyloxy, epoxy, sulfonate, carboxylate, ester, amino, acrylamide, methacrylamide, isocyanato, amino acid, nucleic acid, and mercapto(C 1 -C 6 )alkyl; 
 R b  is independently 
 
       
       
         
           
           
               
               
           
         
         
           wherein: 
           R c  is (C 1 -C 2 )alkyl; 
           R d  is (C 1 -C 2 )alkyl or phenyl; 
           R e  is (C 6 -C 22 )alkyl; 
           X −  is an anion selected from the group consisting of chloride, bromide, fluoride, iodide, sulfonate, and acetate; and 
         
         each R Y  is, independently, H, (C 1 -C 8 )alkyl, or trifluoro-substituted (C 1 -C 8 )alkyl, 
         wherein: 
         each of said particles has a substantially spherical morphology; 
         each of said particle has a substantially ordered lamellar internal structure; and 
         each of said particles is mesoporous; 
       
     
     
         47 . The method of  claim 46 , wherein A 1 , A 2 , A 3 , and A4 are each ethyl. 
     
     
         48 . The method of  claim 47 , wherein R c  and R d  are methyl, and R 3  is octadecyl. 
     
     
         49 . The method of  claim 46 , wherein R a  is a functional group comprising a methacrylate. 
     
     
         50 . The method of  claim 49 , wherein R a  is methacryloxypropyl. 
     
     
         51 . The method of  claim 50 , wherein said trialkoxysilane of formula II is 3-methacryloxypropyltrimethoxysilane (3-MPTS). 
     
     
         52 . A plurality of particles, prepared by the process of  claim 46 .