Silane-Acrylate Chemistry for Regulating Network Formation in Radical Photopolymerization

Photoinitiated silane-ene chemistry has the potential to pave the way toward spatially resolved organosilicon compounds, which might find application in biomedicine, microelectronics, and other advanced fields. Moreover, this approach could serve as a viable alternative to the popular photoinitiated thiol-ene chemistry, which gives access to defined and functional photopolymer networks. A difunctional bis(trimethylsilyl)silane with abstractable hydrogens (DSiH) was successfully synthesized in a simple one-pot procedure. The radical reactivity of DSiH with various homopolymerizable monomers (i.e., (meth)acrylate, vinyl ester, acrylamide) was assessed via ¹H NMR spectroscopic studies. DSiH shows good reactivity with acrylates and vinyl esters. The most promising silane-acrylate system was further investigated in cross-linking formulations toward its reactivity (e.g., heat of polymerization, curing time, occurrence of gelation, double-bond conversion) and compared to state-of-the-art thiol-acrylate resins. The storage stability of prepared resin formulations is greatly improved for silane-acrylate systems vs thiol-ene resins. Double-bond conversion at the gel point (DBC_gel) and overall DBC were increased, and polymerization-induced shrinkage stress has been significantly reduced with the introduction of silane-acrylate chemistry. Resulting photopolymer networks exhibit a homogeneous network architecture (indicated by a narrow glass transition) that can be tuned by varying silane concentration, and this confirms the postulated regulation of radical network formation. Similar to thiol-acrylate networks, this leads to more flexible photopolymer networks with increased elongation at break and improved impact resistance. Additionally, swelling tests indicate a high gel fraction for silane-acrylate photopolymers.