Characterization of alkali-lignin-grafted polyacrylamide synthesized by atom transfer radical polymerization

The preparation of value-added, chemically modified lignin-based copolymers for the use of technical lignin is crucial for green and sustainable development. Herein, we synthesized alkali-lignin-grafted polyacrylamide by atom transfer radical polymerization (ATRP). As alkali lignin (AL) has the highest total hydroxyl group content, it was modified with 2-bromoisobutyryl bromide to synthesize a lignin macroinitiator (lignin-Br) at different ratios of [OH group in AL]:[TEA]:[BiBB] = 1:1:1, 1:1.5:1.5, and 1:2:2. Acrylamide was grafted from lignin-Br with the most Br-initiating sites via ATRP. The ratios of monomer to lignin-Br used were 50:1, 100:1, and 200:1, and the synthesized copolymers (L-g-PAM) were denoted as L-g-PAM50, L-g-PAM100, and L-g-PAM200, respectively. These copolymers were characterized by Fourier transform infrared (FT-IR) and 1H nuclear magnetic resonance (NMR) spectroscopies. The FT-IR and 1H NMR results indicated that polyacrylamide was introduced into the lignin backbone of all L-g-PAM copolymers. Gel permeation chromatography of L-g-PAM showed that the Mw of L-g-PAM200 was the highest at 427,383 g/mol. Photographs and scanning electron microscopy images of L-g-PAM showed that L-g-PAM appeared as a soft sponge and contained interwoven fibers. The maximum degradation temperature (Tmax) of L-g-PAM increased with increasing monomer-to-lignin-Br ratio. Moreover, the glass transition temperature (Tg) of L-g-PAM was higher than that of AL. The alkali-lignin-grafted polyacrylamide, synthesized by ATRP, in our study has a narrow molecular weight distribution, and its soft sponge properties make it a hydrogel or another surfactant.