Functionalized nanoparticles

Abstract

The present invention discloses functionalized nanoparticles comprising on the surface a covalently bound radical of the formula (I) wherein the nanoparticles are SiO 2 , Al 2 O 3 or mixed SiO 2 and Al 2 O 3 nanoparticles, and wherein the general symbols are as defined in claim 1 . These functionalized nanoparticles are for example useful as stabilizers and/or compatibilizers in organic materials, or as photoinitiators in pre-polymeric or pre-crosslinking formulations, or as reinforcer of coatings and improver of scratch resistance in coating compositions for surfaces.

1 . A functionalized nanoparticle comprising on the surface a covalently bound radical of the formula I 
     
       
         
         
             
             
         
       
     
     wherein 
     the nanoparticle is a SiO 2 , Al 2 O 3  or mixed SiO 2  and Al 2 O 3  nanoparticle, 
     X is oxygen, sulfur or 
     
       
         
         
             
             
         
       
     
     R 1  is C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen, sulfur or 
     
       
         
         
             
             
         
       
     
     hydroxyl-substituted 
     C 2 -C 24 alkyl which is interrupted by oxygen, sulfur or 
     
       
         
         
             
             
         
       
     
     C 2 -C 24 alkenyl, C 5 -C 12 cycloalkyl, C 5 -C 12 cycloalkenyl, a polymerizable group, a polymer, or an additive selected from the group consisting of radical scavengers, hydroperoxide decomposers, UV-absorbers, light stabilizers, flame retardants and photoinitiators; 
     R 2  and R 3  independently of each other are hydrogen, C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl, phenyl, C 7 -C 9 phenylalkyl, —OR 5 , 
     
       
         
         
             
             
         
       
     
     R 4  is hydrogen, C 1 -C 25 alkyl or C 3 -C 25 alkyl which is interrupted by oxygen or sulfur; 
     R 5  is hydrogen, C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl, 
     phenyl, C 7 -C 9 phenylalkyl, 
     
       
         
         
             
             
         
       
     
     or the nanoparticle surface, 
     R 6  and R 7  independently of each other are hydrogen, C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl, phenyl, C 7 -C 9 phenylalkyl or —OR 5 , 
     R 8 , R 9  and R 10  independently of each other are hydrogen, C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl, phenyl or C 7 -C 9 phenylalkyl, and 
     n is 1, 2, 3, 4, 5, 6, 7 or 8. 
   
   
       2 . A functionalized nanoparticle according to  claim 1  comprising on the surface additionally a covalently bound radical of the formula II 
     
       
         
         
             
             
         
       
     
     wherein 
     the nanoparticle is a SiO 2 , Al 2 O 3  or mixed SiO 2  and Al 2 O 3  nanoparticle, 
     R 11  is C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen, sulfur or 
     
       
         
         
             
             
         
       
     
     amino-, mercapto- or hydroxyl substituted C 2 -C 24 alkyl; amino-, mercapto- or hydroxyl substituted C 2 -C 24 alkyl which is interrupted by oxygen, sulfur or 
     
       
         
         
             
             
         
       
     
     C 2 -C 24 alkenyl, C 5 -C 12 cycloalkyl, C 5 -C 12 cycloalkenyl, a polymerizable group or a polymer, 
     R 12  and R 13  independently of each other are hydrogen, C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl, phenyl, C 7 -C 9 phenylalkyl, —OR 15 , 
     
       
         
         
             
             
         
       
     
     R 14  is hydrogen, C 1 -C 25 alkyl or C 3 -C 25 alkyl which is interrupted by oxygen or sulfur; 
     R 15  is hydrogen, C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl, phenyl, C 7 -C 9 phenylalkyl, 
     
       
         
         
             
             
         
       
     
     or the nanoparticle surface, 
     R 16  and R 17  independently of each other are hydrogen, C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl, phenyl, C 7 -C 9 phenylalkyl or —OR 15 , 
     R 18 , R 19  and R 20  independently of each other are hydrogen, C 1 -C 25 alkyl, C 3 -C 25 alkyl which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl, phenyl or C 7 -C 9 phenylalkyl. 
   
   
       3 . A functionalized nanoparticle according to  claim 1 , wherein 
     R 1  is an additive selected from the group consisting of phenolic antioxidants, benzofuran-2-ones, sterically hindered amines, aminic antioxidants, 2-(2′-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, 2-(2-hydroxyphenyl)-1,3,5-triazines, phosphites, phosphonites, thioethers, benzophenones, α-activated acetophenones, bisacylphosphinoxides (BAPO), mono-acylphosphinoxides (MAPO), alkoxamines, thioxanthones, benzoins, benzil ketals, benzoin ethers, α-hydroxy-alkylphenones and α-aminoalkylphenones. 
   
   
       4 . A functionalized nanoparticle according to  claim 1 , wherein 
     R 1  is 
     
       
         
         
             
             
         
       
     
     R 24  is C 1 -C 25 alkyl, hydroxyl-substituted C 2 -C 24 alkyl; hydroxyl-substituted C 2 -C 24 alkyl which is interrupted by oxygen, sulfur or 
     
       
         
         
             
             
         
       
     
     C 3 -C 25 alkyl which is interrupted by oxygen, sulfur or 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     R 25  is C 1 -C 25 alkyl or C 2 -C 25 alkenyl, 
     R 26  is hydrogen or methyl, 
     R 27  is hydrogen or methyl, 
     R 28  is hydrogen or 
     
       
         
         
             
             
         
       
     
     R 29  is C 1 -C 4 alkylene, 
     R 30  and R 3 , are each independently of the other hydrogen, C 1 -C 18 alkyl, C 7 -C 9 phenylalkyl, phenyl or C 5 -C 8 cycloalkyl, 
     R 32  and R 33  are each independently of the other hydrogen, C 1 -C 18 alkyl, C 7 -C 9 phenylalkyl, phenyl or C 5 -C 8 cycloalkyl, 
     R 34  and R 35  are each independently of the other hydrogen, halogen, C 1 -C 4 alkyl, —CN, trifluoromethyl or C 1 -C 4 alkoxy, 
     R 36  is a direct bond or —O—, 
     R 37  is hydrogen, —O  , C 1 -C 25 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkinyl, C 1 -C 20 alkoxy, C 5 -C 12 cycloalkoxy, C 7 -C 25 aralkoxy, C 6 -C 12 aryloxy, C 7 -C 9 phenylalkyl, C 5 -C 12 cycloalkyl, phenyl, naphthyl, hydroxyethyl, C 2 -C 25 alkanoyl, benzoyl, naphthoyl or C 2 -C 20 alkoxyalkanoyl, 
     R 38  is hydrogen or an organic radical, 
     R 39  and R 40  are each independently of the other hydrogen, C 1 -C 18 alkyl, C 7 -C 9 phenylalkyl or phenyl, 
     R 41  is hydrogen, halogen or C 1 -C 18 alkyl, 
     R 42  is hydrogen, C 1 -C 18 alkyl or C 7 -C 9 phenylalkyl, 
     R 43  and R 44  are each independently of the other hydrogen, C 1 -C 18 alkyl, C 1 -C 18 alkoxy, 
     di(C 1 -C 4 alkyl)amino, hydroxyl or 
     
       
         
         
             
             
         
       
     
     is hydrogen, C 1 -C 18 alkyl, C 1 -C 18 alkoxy or 
     
       
         
         
             
             
         
       
     
     R 46  and R 47  are each independently of the other hydrogen, hydroxyl, C 1 -C 18 alkyl, phenyl, C 1 -C 18 alkoxy or C 7 -C 9 phenylakyl, 
     R 48  is a direct bond or oxygen, 
     R 49  and R 50  are each independently of the other C 1 -C 18 alkyl, C 7 -C 9 phenylalkyl, cyclohexyl, phenyl, or phenyl substituted by 1 to 3 alkyl radicals having in total 1 to 18 carbon atoms, 
     R 51 , R 52  and R 53  are each independently of the others hydrogen, halogen C 1 -C 4 alkyl or C 1 -C 4 alkoxy, 
     R 54  is C 1 -C 20 alkyl, C 5 -C 8 cycloalkyl, C 7 -C 9 phenylalkyl or phenyl, 
     R 55  is C 1 -C 25 alkyl, 
     R 56  is methylene or ethylene, 
     R 57  is methylene or ethylene, 
     R 62  is hydrogen or C 1 -C 18 alkyl, 
     R 63  and R 64  are each independently of the other hydrogen, C 1 -C 18 alkyl, C 1 -C 18 alkoxy, C 1 -C 4 alkylthio, morpholinyl, C 7 -C 9 phenylalkyl of phenyl, 
     R 65  and R 66  are each independently of the other C 1 -C 18 alkyl, 
     R 67  is C 2 -C 4 alkylene, 
     R 68  is hydrogen or C 1 -C 18 alkyl, 
     R 69  is C 3 -C 7 alkylene, 
     R 70  and R 71  are each independently of the other C 1 -C 8 alkyl or C 7 -C 9 phenylalkyl, 
     R 72  and R 73  are each independently of the other C 1 -C 8 alkyl or R 72  and R 73  are together —CH 2 CH 2 —O—CH 2 CH 2 — thus forming with the nitrogen atom to which they are attached a morpholinyl ring, 
     R 74  is hydrogen, C 1 -C 18 alkyl or C 7 -C 9 phenylalkyl, and 
     x is 1, 2 or 3. 
   
   
       5 . A functionalized nanoparticle according to  claim 1 , wherein n is 3. 
   
   
       6 . A functionalized nanoparticle according to  claim 1 , wherein R 4  is hydrogen or C 1 -C 4 alkyl. 
   
   
       7 . A functionalized nanoparticle according to  claim 2 , wherein 
     R 11  is C 1 -C 18 alkyl, C 3 -C 18 alkyl which is interrupted by oxygen or sulfur; or 3-aminopropyl. 
   
   
       8 . A functionalized nanoparticle according to  claim 1 , wherein the functionalized nanoparticle has a spherical shape. 
   
   
       9 . A functionalized nanoparticle according to  claim 1 , wherein the functionalized nanoparticle has a particle size of 10 to 1000 nm. 
   
   
       10 . A functionalized nanoparticle according to  claim 1 , wherein the functionalized nanoparticle is a silica nanoparticle. 
   
   
       11 . A composition comprising
 a) an organic material subject to oxidative, thermal or light-induced degradation, and   b) at least a functionalized nanoparticle according to  claim 1 .   
   
   
       12 . A composition according to  claim 11 , wherein the composition is a coating composition and component (a) is an organic film-forming binder. 
   
   
       13 . A composition according to  claim 11 , wherein component (a) is a synthetic polymer. 
   
   
       14 . A composition according to  claim 11 , wherein component (b) is present in an amount from 0.01 to 80%, based on the weight of component (a). 
   
   
       15 . A composition according to  claim 11 , wherein additional additives are present besides the components (a) and (b). 
   
   
       16 . A process for stabilizing, flame-retarding and/or compatibilizing an organic material which is subject to oxidative, thermal or light-induced degradation, which comprises incorporating therein, or applying thereto, at least one functionalized nanoparticle according to  claim 1 . 
   
   
       17 . A process for photoinitiating in-situ polymerization or hardening of a pre-polymeric nanocomposite or sol to a nanocomposite material, which comprises incorporating therein, or applying thereto, at least one functionalized nanoparticle according to  claim 1 . 
   
   
       18 - 19 . (canceled) 
   
   
       20 . A process for preparing a reinforced coating with improved scratch resistance on a surface, which comprises treating the surface with a coating composition comprising a functionalized nanoparticle according to  claim 1  and then drying and/or curing the coating composition. 
   
   
       21 . A functionalized nanoparticle according to  claim 1 , wherein 
     the functionalized nanoparticle has a particle size of 10 to 500 nm.