Preparation of Photoresponsive Azo Polymers Based on Lignin, a Renewable Biomass Resource

Lignin-based azo polymers are prepared from alkali lignin, a byproduct in spent liquor from the pulping and papermaking industry, and their structures and photochromic effects are characterized by elemental analysis, Fourier transform infrared, 1H nuclear magnetic resonance, and ultraviolet–visible spectroscopy. Results show that only the 2-(4-nitrophenyl azo) phenol lignin-modified polymer (AL-azo-NO2) shows a significant photochromic effect, and its photoresponsive behavior is evidently slower than that of the synthetic polymer with a similar azo chromophore. For the 2-(4-methoxyphenyl azo) phenol lignin-modified polymer, its photoisomerization behavior was expected to be similar to that of azobenzene-type molecules, but its photoresponse is not obvious. The abnormal photochromic effect of AL-azo polymers is related to strong steric hindrance of lignin backbones. With addition of water (poor solvent), AL-azo-NO2 shrinks gradually, which prevents azobenzene groups from isomerizing and results in a lower isomerization efficiency at higher water contents. Preparation of lignin-based azo polymers offers a novel source of azo polymers and provides a green and sustainable pathway for value-added utilization of lignin biomass recovered from the pulping industry.