Synthesis and catalytic performance of wood cellulose nanofibers grafted with polylactic acid in rare-earth complexes based on tetrazole carboxylic acids

Abstract

Stannous octanoate [Sn(Oct)2] and 4-dimethylamino pyridine (DMAP) were used to catalyze the synthesis of amphiphilic cellulose-based graft copolymers, but the acute toxicity of tin ions and DMAP prompts the need for the application of less harmful catalysts. Herein, green catalyst complexes 1–3 [M(H0.5L)2(H2O)5]·2(H2O) (M = Sm, 1; M = Nd, 2; M = Eu, 3; H2L = 4-(3-(tetrazol-5-yl)pyridin-5-yl)benzoic acid) were synthesized, and their properties were systematically investigated. Single-crystal X-ray diffraction showed that the complexes possessed a zero-dimensional structure, while the thermogravimetry and scanning electron microscopy results confirmed their stability after heating at 110 °C for 10 h. Using complexes 1–3 and DMAP as the catalysts, CNFs were grafted with l-lactide via homogeneous ring-opening polymerization to form wood cellulose nanofibers grafted with l-lactide (WGLAs), and the effects of the ratio of wood cellulose nanofibers (WCNFs) to l-lactide ([AGU]/[LA]) and catalyst dosage were studied. The polymerization followed the coordination–insertion mechanism. Under comparable reaction conditions, the grafting ratio of WGLA-1 reached 84.7 %, and the grafting ratio of complex 1 was found to be higher than those achieved using DMAP. WGLAs demonstrated good thermal stability without cytotoxicity, and the residual catalysts in the WGLAs exhibited fluorescence characteristics. Overall, amphiphilic cellulose-based materials with fluorescence emission offered a promising modification strategy to prepare high-performance polymer composites for agriculture and biomedical application.