Onium salts improve the kinetics of photopolymerization of acrylate activated with visible light

Abstract

The aim was study the influence of onium salts on the kinetics of photopolymerization in the visible light region. Trimethylolpropane triacrylate TMPTA was selected as a monomer, and activated by 1,3-bis(phenylamino)squaraine (SQ) used as a photosensitizer in addition to tetramethylammonium n-butyltriphenylborate (B2). The iodonium salt [A–I–B]⁺X⁻ functioned as a second radical initiator, bearing a different substitution pattern for the cation. The ternary system was formulated with different concentrations of both borate and diphenyliodonium salts. Differential scanning calorimetry was used to investigate the polymerization reaction over the photoactivation time carried out at 300 nm < λ < 500 nm irradiation. When the squaraine dye/borate salt was used as photoinitiator, a slow polymerization reaction was observed and a lower monomer conversion. The addition of a third component (onium salt) increased the polymerization rate and conversion. Ternary photoinitiator systems showed improvement in the polymerization rate of triacrylate leading to high conversion in a short photoactivation time. The photoinitiating ability of bi- and tri-component photoinitiators acting in the UV-Vis region for initiation polymerization of triacrylate was compared with those of some commercially used photoinitiating systems. It was also found, that, the parallel electron transfer from an excited state of the sensitizer to [A–I–B]⁺X⁻, and an electron transfer from a ground state of R(Ph)₃B⁻N(CH₃)₄⁺ to an excited state of the sensitizer results in two types of initiating radical.