Functionalized nanoparticles

Abstract

Functionalized nanoparticles, which are obtainable by combining in a first step a functionalized dyestuff, a silicon-based spacer and a catalyst, and in a second step reacting the product obtained in the first step with a co-reactive organic silicon, aluminum, zirconium or titanium compound. Optionally, the thus obtained functionalized nanoparticles can be combined or encapsulated with a polymer. The functionalized nanoparticles are useful as colorants and fluorescents in plastics, paints, inks, electronic materials, cosmetic articles, and the like.

1 . Functionalized nanoparticles obtained by
 a) combining a functionalized dyestuff of the formula (1a)   
     
       
         
         
             
             
         
       
     
     wherein
 R 1  stands for C 1 -C 18 alkoxy or —OH; 
 R 2 , R 3  independently from each other stand for C 1 -C 18 alkoxy, C 1 -C 18 alkyl or —OH, 
 E stands for a direct bond or a bridging member, 
 D is the residue of a chromophore, and a spacer of the formula (1 b)
   R 4(4-m) SiX m    (1b) 
 
 
     wherein each
 R 4  represents a monovalent organic radical of from 1 to 24 carbon atoms, optionally substituted by a monovalent organic radical, 
 X represents a group capable of undergoing hydrolysis and m is 0, 1, 2, 3 or 4; 
 a catalyst, 
 and optionally a solvent, at time T SB , 
 and treating the obtained mixture until time T SE , wherein (T SE -T SB ) is chosen in the range of from 1 and 48 hours, at a temperature in the range of from 0 to 80° C., 
 b) adding a co-reactive compound (1c) selected from the group consisting of an organic silane, an organic alumina, an organic zirconia and an organic titania, 
 at time T CC , wherein T CC  fulfils either condition (a) T SB <T CC <T SE , condition (b) T CC ≧T SE  or condiition (c) wherein T CC  fulfils both (a) and (b) in case part of co-reactive compound (1c) is added before T SE , and the other part after T SE , 
 and treating the obtained respective reaction mixture for a period of time between 12 and 36 hours at a temperature between 0 and 80° C., and, optionally, after isolating the thus obtained nanoparticles with well-known methods, 
 c) combining the nanoparticles with a polymer or, 
 d) polymerizing a monomer or monomer mixture in the presence of the nanoparticles. 
 
   
   
       2 . Functionalized nanoparticles according to  claim 1 , wherein the co-reactive compound (1c) is added at time T CC ≧T SE  (condition (a)). 
   
   
       3 . Functionalized nanoparticles according to  claim 1 , wherein the co-reactive compound (1c) is added at T CC , wherein T SB <T CC <T SE  (condition (b)). 
   
   
       4 . Functionalized nanoparticles according to  claim 3 , wherein between 10 to 90% by weight of the co-reactive organic compound (1c) is added before T SE , but after T SB , and the residual after or at time T SE  (condition (c)). 
   
   
       5 . Functionalized nanoparticles according to  claim 1 , wherein, in the compound of formula (1b), R 4  is a monovalent radical of from 1 to 12 carbon atoms, which is unsubstituted or substituted by a functional organic group selected from the group consisting of a mercapto, an epoxy, an acrylyl, a methacrylyl, an allyl, a vinyl, a halogeno and an amino group. 
   
   
       6 . Functionalized nanoparticles according to  claim 1 , wherein, in the compound of formula (1b), X stands for C 1 -C 18 alkoxy, whereby the alkyl chain may be interrupted by one or more oxygen or sulphur atoms. 
   
   
       7 . Process for the manufacture of functionalized nanoparticles comprising the steps of:
 a) combining a functionalized dyestuff of the formula (1a)   
     
       
         
         
             
             
         
       
     
     wherein
 R 1  stands for C 1 -C 18 alkoxy or —OH; 
 R 2 , R 3  independently from each other stand for C 1 -C 18 alkoxy, C 1 -C 18 alkyl or —OH, 
 E stands for a direct bond or a bridging member, 
 D is the residue of a chromophore, and a spacer of the formula (1b)
   R 4(4-m) SiX m    (1b) 
 
 
     wherein each
 R 4  represents a monovalent organic radical of from 1 to 24 carbon atoms, optionally substituted by a monovalent organic radical, 
 X represents a group capable of undergoing hydrolysis and m is 0, 1, 2, 3 or 4; 
 a catalyst, 
 and optionally a solvent, at time T SB , 
 and treating the obtained mixture until time T SE , wherein (T SE -T SB ) is chosen in the range of from 1 and 48 hours, at a temperature in the range of from 0 to 80° C., 
 b) adding a co-reactive compound (1c) selected from the group consisting of an organic silane, an organic alumina, an organic zirconia and an organic titania, 
 at time T CC , wherein T CC  fulfils either condition (a) T SB <T CC <T SE , condition (b) T CC ≧T SE  or condiition (c) wherein T CC  fulfils both (a) and (b) in case part of co-reactive compound (1c) is added before T SE , and the other part after T SE , 
 and treating the obtained respective reaction mixture for a period of time between 12 and 36 hours at a temperature between 0 and 80° C., 
 and, optionally, after isolating the thus obtained nanoparticles with well-known methods, 
 c) combining the nanoparticles with a polymer or, 
 d) polymerizing a monomer or monomer mixture in the presence of the nanoparticles. 
 
   
   
       8 . (canceled) 
   
   
       9 . A composition comprising the functionalized nanoparticles according to  claims 1  and an organic material. 
   
   
       10 . Functionalized nanoparticles according to  claim 5 , wherein, in the compound of formula (1b), X stands for C 1 -C 18 alkoxy, whereby the alkyl chain may be interrupted by one or more oxygen or sulphur atoms.