Polymerizable organosilicon nanocapsules

Abstract

The present invention provides a polymerizable organosilicon nanocapsule, which includes: a nanoscale core A, which includes: at least one particle comprising at least one oxide or mixed oxide, KA—O, of at least one metal or semimetal selected from the group including main groups 2 to 6 of the Periodic Table, transition groups 1 to 8 of the Periodic Table, lanthanides, and mixtures thereof; and an organosilicon shell B, which includes: at least one organosilicon compound having the formula (Ia): (Si′O—) x Si—R  (Ia)  wherein R is a vinyl or allyl group;  wherein x is a number from 0 to 20;  wherein remaining free valences of Si are each independently (KA—O)—, SiO— or —Z;  wherein remaining free valences of Si′ are each independently (KA—O)—, SiO—, —R, or  wherein the Z's are each independently hydroxyl or alkoxy radicals; and  wherein each Si and Si′ in the shell B have not more than one R group attatched thereto.

1 . A polymerizable organosilicon nanocapsule, comprising: 
 a nanoscale core A, which comprises: 
 at least one particle comprising at least one oxide or mixed oxide, KA—O, of at least one metal or semimetal selected from the group consisting of main groups 2 to 6 of the Periodic Table, transition groups 1 to 8 of the Periodic Table, lanthanides, and mixtures thereof; and  
   an organosilicon shell B, which comprises: 
 at least one organosilicon compound having the formula (Ia):  
 (Si′O—) x Si—R  (Ia)  
  wherein R is a vinyl or allyl group;  
  wherein x is a number from 0 to 20;  
  wherein remaining free valences of Si are each independently (KA—O)—, SiO— or —Z;  
  wherein remaining free valences of Si′ are each independently (KA—O)—, SiO—, —R, or  
  wherein the Z's are each independently hydroxyl or alkoxy radicals; and  
  wherein each Si and Si′ in the shell B have not more than one R group attatched thereto.  
   
     
     
         2 . The nanocapsule according to  claim 1 , wherein said nanocapsule has the following formula (Ib):  
       (KA—O)—{(Si′O—) x (Si—R}  (Ib)  wherein R is a vinyl or allyl group;    wherein x is a number from 0 to 20;    wherein the remaining free valences of Si are each independently KA—O, SiO— or —Z;    wherein the remaining free valences of Si′ are each independently KA—O, SiO—, —R, or —Z;    wherein the Z's are each independently hydroxyl or alkoxy radicals;    and wherein each Si and Si′ in the shell B have not more than one R group attatched directly thereto.    
     
     
         3 . The nanocapsule according to  claim 1 , wherein said organosilicon compound of the shell B is attached to said KA—O core A (KA—O) by one or more covalent linkages.  
     
     
         4 . The nanocapsule according to  claim 1 , wherein the core A is an oxide and/or mixed oxide (KA—O) of an element selected from the group consisting of Si, Al, Ti and Zr.  
     
     
         5 . The nanocapsule according to  claim 1 , wherein said nanocapsule has an average diameter of from 10 to 400 nm.  
     
     
         6 . The nanocapsule according to  claim 1 , wherein the core A has an average particle diameter of from 1 to 100 nm.  
     
     
         7 . The nanocapsule according to  claim 1 , wherein at least one of the free valencies of Si or Si′ or both in said shell is (KA—O).  
     
     
         8 . The nanocapsule according to  claim 1 , wherein said shell is not covalently bonded to said core KA—O.  
     
     
         9 . A composition, comprising the nanocapsule according to  claim 1  and at least one selected from the group consisting of a liquid, a curable synthetic resin, a precursor of a synthetic resin, and a mixture thereof.  
     
     
         10 . The composition according to  claim 9 , which is a coating composition or coating material.  
     
     
         11 . The composition according to  claim 9 , wherein the curable synthetic resin or precursor of a curable synthetic resin comprises at least one selected from the group consisting of acrylate, methacrylate, epoxide, epoxy resin, polyurethane, polyurethane resin, unsaturated polyester, unsaturated polyester resin, epoxy acrylate, polyester acrylate, urethane acrylate, silicone acrylate, and mixtures thereof.  
     
     
         12 . A process, which comprises applying the composition according to  claim 9  to a substrate.  
     
     
         13 . The process according to  claim 12 , further comprising subjecting the coated substrate to photochemical curing.  
     
     
         14 . The process according to  claim 12 , which is a process for producing a scratch-resistant coating.  
     
     
         15 . The process according to  claim 13 , wherein said photochemical curing comprises curing with UV radiation or electron beams at a temperature ranging from 10 to 60° C.  
     
     
         16 . A composition, comprising the nanocapsule according to  claim 1  and a cured resin, wherein said cured resin comprises at least one selected from the group consisting of acrylate, methacrylate, epoxide, epoxy resin, polyurethane, polyurethane resin, unsaturated polyester, unsaturated polyester resin, epoxy acrylate, polyester acrylate, urethane acrylate, silicone acrylate, and mixtures thereof.  
     
     
         17 . The composition according to  claim 16 , wherein the core A has an SiO 2  content of up to 60% by weight, based on the composition.  
     
     
         18 . The composition according to  claim 16 , which is a scratch-resistant coating.  
     
     
         19 . A coated article, comprising the composition according to  claim 16  in contact with a substrate.  
     
     
         20 . The coated article according to  claim 19 , wherein said substrate is selected from the group consisting of sheetlike substrate, paper, metal foil, polymer film, metal, aluminum, iron, steel, brass, copper, silver, magnesium, nonferrous metal alloy, wood, board, textile, stone, plastic, thermoplastic, polycarbonate, glass, ceramic and combinations thereof.  
     
     
         21 . The coated article according to  claim 19 , which is selected from the group consisting of decorative paper, aluminum foil, polycarbonate auto glazing, PVC window frame, door, furniture, and worktop.  
     
     
         22 . A polymerizable organosilicon nanocapsule prepared by a process, comprising reacting: 
 (i) at least one nanoscale oxide and/or mixed oxide (KA—O) particle of at least one metal or semimetal selected from the group consisting of main groups two to six of the Periodic Table of the Elements, transition groups one to eight of the Periodic Table of the Elements, lanthanides, and combinations thereof, with    (ii) at least one vinyltrialkoxysilane and/or allyltrialkoxysilane, alkoxy being a methoxy, ethoxy, n-propoxy or i-propoxy group, and    (iii) optionally, at least one monomeric and/or oligomeric silicic ester which carries at least one selected from the group consisting of methoxy, ethoxy, n-propoxy, i-propoxy group, and combinations thereof and has an average degree of oligomerization of from 1 to 50, and    (iv) optionally, at least one organofunctional siloxane whose functionalities are identical or different and in which each silicon atom independently carries at least one functionality selected from the group consisting of alkyl, fluoroalkyl, cyanoalkyl, isocyanoalkyl, alkenyl, aminoalkyl, diaminoalkyl, triaminoalkyl, alkoxyalkyl, hydroxyalkyl, acylalkyl, glycidyloxyalkyl, acryloyloxyalkyl, methacryloyloxyalkyl, mercaptoalkyl, ureidoalkyl, aryl, alkoxy, and combinations thereof, and remaining free valences of the silicon atoms in the siloxane are satisfied by methoxy or ethoxy or hydroxyl groups, and    (v) optionally, a further organofunctional silane having the formula II:    R′ s R″ r SiY (4-s-r)   (II),     in which the groups R′ and R″ are identical or different and are each independently selected from the group consisting of a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, chloroalkyl, bromoalkyl, iodoalkyl, isocyanoalkyl, cyanoalkyl, fluoroalkyl, perfluoroalkyl, alkenyl, aryl, acylalkyl, acryloyloxyalkyl, methacryloyloxyalkyl, sulfane, mercaptoalkyl, thiacyamidoalkyl, glycidyloxyalkyl, aminoalkyl, diaminoalkyl, triaminoalkyl, carbonatoalkyl or ureidoalkyl group, the respective alkylene groups containing 1 to 6 carbon atoms, Y is a methoxy, ethoxy, i-propoxy, n-propoxy or 2-methoxyethoxy group, s is 1 or 2 or 3, and r is 0 or 1 or 2, subject to the proviso that (s+r)≦3,     wherein said reacting is carried out in situ in a liquid, a curable synthetic resin or a precursor of a synthetic resin.    
     
     
         23 . The nanocapsule according to  claim 22 , wherein the nanoscale oxide and/or mixed oxide (KA—O) is an oxide and/or mixed oxide of an element selected from the group consisting of Si, Al, Ti and Zr.  
     
     
         24 . The nanocapsule according to  claim 22 , which has an average diameter of from 110 to 400 nm.  
     
     
         25 . The nanocapsule according to  claim 22 , wherein the curable synthetic resin or precursor of a curable synthetic resin comprises at least one selected from the group consisting of acrylate, methacrylate, epoxide, epoxy resin, polyurethane, polyurethane resin, unsaturated polyester, unsaturated polyester resin, epoxy acrylate, polyester acrylate, urethane acrylate, silicone acrylate, and mixtures thereof.  
     
     
         26 . A process for preparing a polymerizable organosilicon nanocapsule, comprising reacting: 
 (i) at least one nanoscale oxide and/or mixed oxide (KA—O) particle of at least one metal or semimetal selected from the group consisting of main groups two to six of the Periodic Table of the Elements, transition groups one to eight of the Periodic Table of the Elements, lanthanides, and combinations thereof, with    (ii) at least one vinyltrialkoxysilane and/or allyltrialkoxysilane, alkoxy being a methoxy, ethoxy, n-propoxy or i-propoxy group, and (iii) optionally, at least one monomeric and/or oligomeric silicic ester which carries at least one selected from the group consisting of methoxy, ethoxy, n-propoxy, i-propoxy group, and combinations thereof and has an average degree of oligomerization of from 1 to 50, and    (iv) optionally, at least one organofunctional siloxane whose functionalities are identical or different and in which each silicon atom independently carries at least one functionality selected from the group consisting of alkyl, fluoroalkyl, cyanoalkyl, isocyanoalkyl, alkenyl, aminoalkyl, diaminoalkyl, triaminoalkyl, alkoxyalkyl, hydroxyalkyl, acylalkyl, glycidyloxyalkyl, acryloyloxyalkyl, methacryloyloxyalkyl, mercaptoalkyl, ureidoalkyl, aryl, alkoxy, and combinations thereof, and remaining free valences of the silicon atoms in the siloxane are satisfied by methoxy or ethoxy or hydroxyl groups, and    (v) optionally, a further organofunctional silane having the formula II:    R′ s R″ r SiY (4-s-r)   (II),     in which the groups R′ and R″ are identical or different and are each independently selected from the group consisting of a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, chloroalkyl, bromoalkyl, iodoalkyl, isocyanoalkyl, cyanoalkyl, fluoroalkyl, perfluoroalkyl, alkenyl, aryl, acylalkyl, acryloyloxyalkyl, methacryloyloxyalkyl, sulfane, mercaptoalkyl, thiacyamidoalkyl, glycidyloxyalkyl, aminoalkyl, diaminoalkyl, triaminoalkyl, carbonatoalkyl or ureidoalkyl group, the respective alkylene groups containing 1 to 6 carbon atoms, Y is a methoxy, ethoxy, i-propoxy, n-propoxy or 2-methoxyethoxy group, s is 1 or 2 or 3, and r is 0 or 1 or 2, subject to the proviso that (s+r)≦3,     wherein said reacting is carried out in situ in a liquid, a curable synthetic resin or a precursor of a synthetic resin.    
     
     
         27 . The process as claimed in  claim 26 , wherein the nanoscale oxide and/or mixed oxide (KA—O) has an average particle diameter of from 1 to 100 nm.  
     
     
         28 . The process as claimed in  claim 26 , wherein the curable synthetic resin or precursor of a curable synthetic resin comprises at least one selected from the group consisting of acrylate, methacrylate, epoxide, epoxy resin, polyurethane, polyurethane resin, unsaturated polyester, unsaturated polyester resin, epoxy acrylate, polyester acrylate, urethane acrylate, silicone acrylate, and mixtures thereof.  
     
     
         29 . The process as claimed in  claim 26 , wherein from 0.1 to 60% by weight of nanoscale oxide and/or mixed oxide (KA—O) is present, based on the weight of the synthetic resin.  
     
     
         30 . The process as claimed in  claim 26 , wherein (i) and at least one selected from the group consisting of (ii), (iii), (iv) and (v) are employed in a weight ratio ranging from 4:1 to 1:1.  
     
     
         31 . The process as claimed in  claim 26 , wherein the reaction is conducted in the presence of a catalyst.  
     
     
         32 . The process as claimed in  claim 26 , wherein the reaction is conducted in the presence of water.  
     
     
         33 . The process as claimed in  claim 26 , wherein the reaction is conducted in the presence of a wetting agent.  
     
     
         34 . The process as claimed in  claim 26 , wherein the reaction is conducted at a temperature ranging from 30 to 100° C.  
     
     
         35 . The process as claimed in  claim 26 , wherein 
 the curable synthetic resin or a precursor of a curable synthetic resin is introduced heated,    catalyst, optionally, a wetting agent and water are added,    components (ii) to (v) are introduced, and then    component (i) is added with mixing.    
     
     
         36 . The process as claimed in  claim 26 , further comprising removing alcohol from the reaction system during the reaction, after the reaction, or both.  
     
     
         37 . A process for preparing a composition based on a curable synthetic resin and comprising polymerizable organosilicon nanocapsules, the process comprising: 
 heating the curable synthetic resin or a precursor of the curable synthetic resin,    adding catalyst, optionally, a wetting agent and water,    adding at least one organosilicon component of the formula III:    R 1 R 2   n SiX 3-n   (III)     where the groups R 1  and R 2  are identical or different, R 1  is an alkenyl group having 2 to 18 carbon atoms, an aryl, alkylaryl, an arylalkyl, an acylalkyl, an aminoalkyl, a diaminoalkyl, a triaminoalkyl, an alkyloxyalkyl, an acylalkyl, a cyanoalkyl, an isocyanoalkyl, a glycidyloxyalkyl, an acyloxyalky, an acryloyloxyalkyl, a mercaptoalkyl, a polysulfide-alkyl or a methacryloyloxyalkyl group, and R 2  possesses the same definition as R 1  or is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted, and     optionally, a monomeric and/or oligomeric silicic ester which carries at least one selected from the group consisting of methoxy, ethoxy, n-propoxy, i-propoxy group and combinations thereof and has an average degree of oligomerization of from 1 to 50, and     optionally, an organofunctional siloxane whose functionalities are identical or different and in which each silicon atom in the siloxane carries at least one functionality selected from the group consisting of alkyl, fluoroalkyl, cyanoalkyl, isocyanoalkyl, alkenyl, aminoalkyl, diaminoalkyl, triaminoalkyl, alkoxyalkyl, hydroxyalkyl, acylalkyl, glycidyloxyalkyl, acryloyloxyalkyl, methacryloyloxyalkyl, mercaptoalkyl, ureidoalkyl, aryl, alkoxy, methoxy, ethoxy, and combinations thereof, and remaining free valences of the silicon atoms in the siloxane are satisfied by methoxy or ethoxy or hydroxyl groups,     mixing and then adding at least one nanoscale oxide and/or mixed oxide (KA—O) particle of at least one metal or semimetal selected from the group consisting of main groups 2 to 6, of the Periodic Table of the Elements, transition groups 1 to 8 of the Periodic Table of the Elements, lanthanides, and mixtures thereof with thorough mixing, and     removing alcohol formed by hydrolysis and/or condensation.    
     
     
         38 . The process as claimed in  claim 37 , wherein the organosilicon component of the formula III is selected from the group consisting of 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxy-2-methylpropyltrimethoxysilane, 3-methacryloyloxy-2-methylpropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinylmethyl diethoxysilane.  
     
     
         39 . The process as claimed in  claim 37 , wherein a nanoscale silica is used as oxide component (KA—O).  
     
     
         40 . The process as claimed in  claim 37 , wherein from 0.5 to 6 mol of water are used per mole of Si of the organosilicon component of the formula III.