High-efficient lignin-based polymerizable macromolecular photoinitiator with UV-blocking property for visible light polymerization

Developing high-efficient visible light macromolecular photoinitiator (macro PI) with excellent initiation performance, low migration, high biosafety and multi-function is beneficial to broaden the application of photopolymer. Lignin contains chromophores which could generate free radicals under light irradiation. In this study, a lignin-based polymerizable macro PI (DAL-11ene-amine) was designed and synthesized through covalent grafting 10-undecenoyl chloride (11ene) and hydrogen donor 4-(dimethylaminobenzoic acid) ethyl ester (EDAB) into dealkaline lignin (DAL) skeleton. The structure of DAL-11ene-amine was characterized by UV–vis, FTIR , 1 H NMR, GPC , and 31 P NMR spectra. Under the irradiation of a 405 nm LED, DAL-11ene-amine can directly produce active species and initiate the polymerization of acrylate monomers or thiol-ene click reaction. The photoinitiation efficiency of DAL-11ene-amine is higher than that of DAL-11ene or the two-component combination of DAL-11ene and EDAB. Using DAL-11ene-amine as PI, the prepared polymer films exhibit excellent UV-blocking property. With only 0.5 wt% addition of DAL-11ene-amine, nearly 100% of UVB + UVC and the most of UVA can be blocked by the films. Moreover, DAL-11ene-amine exhibits higher migration stability and biosafety because it can be covalently linked into polymer cross-linking networks. The results indicate that DAL-11ene-amine has great application potentials in preparing environmentally friendly UV-blocking films and biosafety coatings.