In
this paper, we report the synthesis and structural characterization
of transparent and photopolymerizable aluminum-phosphate-silicate
hybrid materials obtained via the sol–gel route, with different
aluminum/phosphate (Al/P) ratios. We explored the system Si(1–x)–(Al/P) (x) with
x varying from 0.3 to 1, and atomic ratios of Al/P are 1:3, 1:1, and
3:1. All compositions contain high inorganic mass content (up to 40
wt %). Furthermore, they are compatible with vat-photopolymerization
platforms. The structural evolution of the hybrid materials with the
silicon concentration was investigated by SEM, phase-contrast AFM,
and solid-state NMR techniques, using single- and double-resonance
experiments. The structure follows the build-up principle using aluminum-phosphate
species and alkoxysilane chains as fundamental building blocks. These
aluminum-phosphate species were identified as monomeric and dimeric
chain structures by comparing different parameters obtained from NMR
data to compound models. Monomeric and dimeric aluminum-phosphate
chain structures were predominant in 3:1 and 1:3 Al/P ratio samples,
respectively, promoting and hindering the heterocondensation with
the alkoxysilane precursor, respectively. The photopolymerization
mechanism leads to the percolation of the inorganic networks through
a parallel polymethylmethacrylate network, resulting in a material
with structural heterogeneities in the range of 5 nm, evidenced by
phase-contrast AFM.