High Refractive Index Photopolymers by Thiol-Yne "Click" Polymerization

A scalable synthesis of high refractive index, optically transparent photopolymers from a family of low-viscosity multifunctional thiol and alkyne monomers via thiol-yne "click" is described herein. The monomers designed to incorporate high refractive index cores consisting of aryl and sulfide groups with high intrinsic molar refraction were synthesized starting from commercially available low-cost raw materials. The low-viscosity (<500 cP) thiol-yne resins formulated with these new multifunctional monomers and a phosphine oxide photoinitiator underwent efficient thiol-yne polymerizations upon exposure to 405 nm light at 30 mW/cm². In contrast to the previously reported thiol-ene systems, the kinetic profile of these photopolymerizations showed significant dependence on the nature of the thiol and alkyne monomers. However, the ability of the thiol-yne reaction to introduce a large number of sulfide linkages compared to that of thiol-ene systems yielded cross-linked high optical quality photopolymers with a polymer refractive index that exceeds 1.68 (n_D/20 °C). Interestingly, the photopolymer formed from the least sterically hindered alkynyl thioether monomer 2b with flexible thioether core and the dithiol 1a exhibited unprecedented difference in the polymer refractive index as compared to that of the resin with polymerization-induced changes reaching up to 0.08. Furthermore, the implementation of these low-viscosity thiol-yne resins was demonstrated by preparing two-stage photopolymeric holographic materials with a dynamic range of ∼0.02 and haze < 1.5% in two-dimensional high refractive index structures.