Functionalized vinyl polymer nanoparticles

Abstract

Nanoparticles of functionalised, cross-linked vinyl polymer, usable as reinforcing filler in a polymeric matrix. The vinyl polymer is a copolymer of at least the following monomers, which are all copolymerisable by free-radical polymerisation: a non-aromatic vinyl monomer “A”; a monomer “B” bearing a function Z of formula ≡Si—X, where X represents a hydroxyl or hydrolysable group; and a cross-linking monomer “C” which is at least bifunctional from the point of view of the polymerisation. The vinyl polymer is preferably a polymethacrylate, in particular a copolymer of methyl methacrylate (monomer A), trimethoxysilylpropyl methacrylate (monomer B) and ethylene glycol dimethacrylate (monomer C), being in the form of nanobeads the diameter of which is of between 10 and 100 nm.

1 . Nanoparticles of functionalised, cross-linked vinyl polymer, usable as reinforcing filler in a polymeric matrix, characterised in that said vinyl polymer is a copolymer of at least the following monomers, which are all copolymerisable by free-radical polymerisation:
 a non-aromatic vinyl monomer “A”:   a monomer “B” bearing a function Z of formula δSi—X, X representing a hydroxyl or hydrolysable group; and   a cross-linking monomer “C”, which is at least bifunctional from the point of view of said polymerisation.   
     
     
         2 . Nanoparticles according to  claim 1 , X being a halogen. 
     
     
         3 . Nanoparticles according to  claim 2 , X being chlorine. 
     
     
         4 . Nanoparticles according to  claim 1 , X corresponding to the formula OR in which R represents hydrogen or a straight-chain or branched monovalent hydrocarbon group. 
     
     
         5 . Nanoparticles according to  claim 4 , R being selected from the group consisting of hydrogen, alkyls, alkoxyalkyls, cycloalkyls and aryls, said alkyls and aryls comprising from 1 to 15 carbon atoms. 
     
     
         6 . Nanoparticles according to  claim 5 , R being selected from the group consisting of hydrogen, C 1 -C 8  alkyls, C 2 -C 8  alkoxyalkyls, C 5 -C 10  cycloalkyls and C 6 -C 12  aryls. 
     
     
         7 . Nanoparticles according to  claim 6 , Z corresponding to one of the formulae: 
       
         
           
           
               
               
           
         
       
       in which:
 the radicals R 1 , which may or may not be substituted, and which may be identical or different, are selected from the group consisting of C 1 -C 8  alkyls, C 5 -C 5  cycloalkyls and C 6 -C 12  aryls; 
 the radicals R 2 , which may or may not be substituted, and which may be identical or different, are selected from the group consisting of hydroxyl, C 1 -C 8  alkoxyls and C 5 -C 8  cycloalkoxyls. 
 
     
     
         8 . Nanoparticles according to  claim 7 , the radicals R 1  being selected from the group consisting of C 1 -C 4  alkyls, cyclohexyl and phenyl. 
     
     
         9 . Nanoparticles according to  claim 8 , the radicals R 1  being selected from the group consisting of C 1 -C 4  alkyls. 
     
     
         10 . Nanoparticles according to  claim 7 , the radicals R 2  being selected from the group consisting of hydroxyl and C 1 -C 6  alkoxyls. 
     
     
         11 . Nanoparticles according to  claim 10 , the radicals R 2  being selected from the group consisting of hydroxyl and C 1 -C 4  alkoxyls. 
     
     
         12 . Nanoparticles according to  claim 11 , the radicals R 1  being selected from among methyl and ethyl and the radicals R 2  being selected from the group consisting of hydroxyl, methoxyl and ethoxyl. 
     
     
         13 . Nanoparticles according to  claim 1 , the majority weight fraction of the copolymer being a non-aromatic vinyl fraction. 
     
     
         14 . Nanoparticles according to  claim 1 , the monomer A bearing one or more, preferably a single, function(s) polymerisable by free-radical polymerisation. 
     
     
         15 . Nanoparticles according to  claim 14 , the monomer A corresponding to Formula (II): 
       
         
           
           
               
               
           
         
       
       in which:
 the radical R 3  is selected from the group consisting of hydrogen, C 1 -C 8  alkyls and C 5 -C 8  cycloalkyls; 
 the radical Y is selected from the group consisting of halogens, the radicals OH, OR′, SR′, C≡N, C(O)OH, C(O)OR′, C(O)N(R′R″), C(O)R′ and OC(O)R′ in which R′ and R″, which may be identical or different, are selected from the group consisting of alkyls comprising from 1 to 12 carbon atoms, and aryls, aralkyls or alkaryls comprising from 6 to 20 carbon atoms. 
 
     
     
         16 . Nanoparticles according to  claim 15 , Formula (II) satisfying the following characteristics:
 R 3  is selected from the group consisting of hydrogen and C 1 -C 4  alkyls;   Y is selected from the group consisting of chlorine, the radicals C(O)OH, C(O)OR′, C(O)N(R′R″) and OC(O)R′.   
     
     
         17 . Nanoparticles according to  claim 16 , Formula (II) satisfying the following characteristics:
 R 3  is hydrogen or methyl;   Y is the C(O)OR′ group in which R′ is preferably an alkyl comprising from 1 to 8 carbon atoms.   
     
     
         18 . Nanoparticles according to  claim 17 , the monomer A being selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert. butyl acrylate, tert. butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate and mixs of these compounds. 
     
     
         19 . Nanoparticles according to  claim 18 , the monomer A being methyl acrylate or methacrylate, preferably methyl methacrylate. 
     
     
         20 . Nanoparticles according to  claim 1 , the monomer B being selected from the group consisting of hydroxysilyl-(C 1 -C 4 ) alkyl acrylates, hydroxysilyl-(C 1 -C 4 ) alkyl methacrylates, (C 1 -C 4 ) alkoxysilyl-(C 1 -C 4 ) alkyl acrylates, (C 1 -C 4 ) alkoxysilyl-(C 1 -C 4 ) alkyl methacrylates and mixs of these compounds. 
     
     
         21 . Nanoparticles according to  claim 20 , the monomer B being selected from the group consisting of hydroxysilyl-(C 1 -C 4 ) alkyl acrylates, hydroxysilyl-(C 1 -C 4 ) alkyl methacrylates, methoxysilyl-(C 1 -C 4 ) alkyl acrylates, methoxysilyl-(C 1 -C 4 ) alkyl methacrylates, ethoxysilyl-(C 1 -C 4 ) alkyl acrylates, ethoxysilyl-(C 1 -C 4 ) alkyl methacrylates and mixs of these compounds. 
     
     
         22 . Nanoparticles according to  claim 21 , the monomer B being selected from the group consisting of hydroxysilylpropyl acrylates, hydroxysilylpropyl methacrylates, methoxysilylpropyl acrylates, methoxysilylpropyl methacrylates, ethoxysilylpropyl acrylates, ethoxysilylpropyl methacrylates and mixs of these compounds. 
     
     
         23 . Nanoparticles according to  claim 22 , the comonomer B being trimethoxysilylpropyl acrylate or methacrylate. 
     
     
         24 . Nanoparticles according to  claim 1 , the comonomer B being selected from the group consisting of styryl-(C 1 -C 4 ) alkyl-hydroxysilanes, styryl-(C 1 -C 4 ) alkyl-(C 1 -C 4 ) alkoxysilanes and mixs of these compounds. 
     
     
         25 . Nanoparticles according to  claim 24 , the comonomer B being selected from the group consisting of styryl-(C 1 -C 4 ) alkyl-hydroxysilanes, styryl-(C 1 -C 4 ) alkyl-methoxysilanes, styryl-(C 1 -C 4 ) alkyl-ethoxysilanes and mixs of these compounds. 
     
     
         26 . Nanoparticles according to  claim 25 , the comonomer B being selected from the group consisting of styrylethylhydroxysilanes, styrylethylmethoxysilanes, styrylethylethoxysilanes and mixs of these compounds. 
     
     
         27 . Nanoparticles according to  claim 26 , the comonomer B being styrylethyltrimethoxysilane. 
     
     
         28 . Nanoparticles according to  claim 1 , the molar ratio of comonomer B in said vinyl polymer being greater than 5%. 
     
     
         29 . Nanoparticles according to  claim 28 , the molar ratio of comonomer B in said vinyl polymer being between 5 and 30%. 
     
     
         30 . Nanoparticles according to  claim 29 , the molar ratio of comonomer B in said vinyl polymer being between 5 and 20%. 
     
     
         31 . Nanoparticles according to  claim 1 , the comonomer C bearing at least two polymerisable unsaturated groups. 
     
     
         32 . Nanoparticles according to  claim 31 , the polymerisable unsaturated groups being ethylene groups. 
     
     
         33 . Nanoparticles according to  claim 1 , the vinyl polymer being obtained by free-radical polymerisation. 
     
     
         34 . Nanoparticles according to  claim 1 , the comonomer C being selected from the group consisting of polyol diacrylates, polyol triacrylates, polyol dimethacrylates, polyol trimethacrylates, alkylene diacrylamides, alkylene dimethacrylamides, vinyl aromatic compounds bearing at least two vinyl groups, and mixs of these compounds. 
     
     
         35 . Nanoparticles according to  claim 34 , the comonomer C being a styrene compound. 
     
     
         36 . Nanoparticles according to  claim 35 , the styrene compound being selected from the group consisting of diisopropenylbenzene, divinylbenzene, trivinylbenzene and mixs of these compounds. 
     
     
         37 . Nanoparticles according to  claim 34 , the comonomer C being selected from the group consisting of polyol diacrylates, polyol dimethacrylates and mixs of these compounds. 
     
     
         38 . Nanoparticles according to  claim 37 , the comonomer C being selected from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, hexamethylene glycol diacrylate, hexamethylene glycol dimethacrylate and mixs of these compounds. 
     
     
         39 . Nanoparticles according to  claim 1 , the weight ratio of comonomer C in said vinyl polymer being greater than 5%. 
     
     
         40 . Nanoparticles according to  claim 39 , the weight ratio of monomer C in said vinyl polymer being between 10 and 30%. 
     
     
         41 . Nanoparticles according to  claim 40 , the weight ratio of monomer B being between 10 and 30%. 
     
     
         42 . Nanoparticles according to  claim 41 , the weight ratio of monomer B being between 20 and 30%. 
     
     
         43 . Nanoparticles according to  claim 1 , the average diameter of the nanoparticles being between 10 and 100 nm. 
     
     
         44 . Nanoparticles according to  claim 43 , the average diameter of the nanoparticles being between 10 and 60 nm. 
     
     
         45 . Nanoparticles according to  claim 38 , the vinyl polymer being a copolymer of methyl methacrylate (monomer A), trimethoxysilylpropyl methacrylate (monomer B) and ethylene glycol dimethacrylate (monomer C). 
     
     
         46 . The use of nanoparticles according to  claim 1  for reinforcing a polymeric matrix. 
     
     
         47 . The use according to  claim 46 , the polymer of the polymeric matrix being an elastomer. 
     
     
         48 . The use according to  claim 46 , for the reinforcement of tyres. 
     
     
         49 . A masterbatch comprising nanoparticles according to  claim 1 , embedded in a polymeric matrix. 
     
     
         50 . A masterbatch according to  claim 49 , the polymer of the polymeric matrix being an elastomer. 
     
     
         51 . A polymeric composition comprising at least one polymer, nanoparticles according to  claim 1 , and a coupling agent providing the bond between the polymer and the surface of the nanoparticles.