Inorganic-organic hybrids polymers from surface-modified oxo-metallate clusters

Inorganic-organic hybrid polymers were prepared by radical polymerization of methacrylic acid or methyl methacrylate with the (meth) acrylate-substituted oxozirconium and oxotitanium clusters Zr6(OH)4O4(OMc)12(OMc = methacrylate), Zr4O2(OMc)12, Ti6O4(OEt)8(OMc)8 and Ti4O2(OPri)6(OAcr)6(OAcr = acrylate). A few mol% of cluster is sufficient for an efficient cross-linking of the polymer chains. Small-angle X-ray scattering data indicate that the cluster size is retained in the polymers and that the microstructure of the cluster cross-linked samples can be described by a dispersion of identical spherical or disk-shaped clusters in the polymer. The obtained hybrid polymers exhibit a higher thermal stability because depolymerization reactions are inhibited. Contrary to undoped poly (methyl methacrylate), the cluster cross-linked polymers are insoluble but swell in organic solvents. The solvent uptake upon swelling decreases with an increasing amount of polymerized cluster.