Mechanistic insight into homogeneous catalytic crosslinking behavior between cellulose and epoxide by explicit solvent models.

Inspired by recent advances on functional modification of cellulosic materials, the crosslinking behaviors of epoxide with cellulose under the catalysis of different homogeneous catalysts including H 2 O, Brønsted acid, Brønsted base, Lewis acid and neutral salt were systematically investigated using density functional theory (DFT) methods with hybrid micro-solvation-continuum approach. The results showed that catalytic activity, reaction mechanism and regioselectivity are determined by the combined effect of catalyst type, electronic effect and steric hindrance. All the homogeneous catalysts have catalytic activity for the crosslinking reaction, which decreases in the order of NaOH > HCl > N Cl 3 > M Cl 2 > CH 3 COOH > NaCl (N = Fe3+, Al3+; M = Zn2+, Ca2+). Upon the catalysis of NaOH, hydroxyl group of cellulose is firstly deprotonated to form a carbanion-like intermediate which will further attack the less sterically hindered C atom of epoxide showing excellent regioselectivity. Acidic catalysts readily cause epoxide protonated, which suffers from nucleophilic attack of cellulose and forms the carbocation-like intermediate. Brønsted acid exhibits poor regioselectivity, however, Lewis acid shows an interesting balance between catalytic activity and regioselectivity for the crosslinking reaction, which may be attributed to the unique catalysis and stabilization effects of its coordinated H 2 O on the transition state structure. [Display omitted] • Catalytic activation decreases in the order of NaOH > HCl > N Cl 3 > M Cl 2 > CH 3 COOH > NaCl. • Mechanism, reactivity and regioselectivity depend on catalyst type, electronic effect and steric hindrance. • Lewis acid is suggested in the hydrated form where the coordinated H 2 O has unique catalysis and stabilization effect. • Lewis acid exhibits an interesting balance between catalytic activation and regioselectivity. • The less sterically hindered carbon atom of epoxide prefers to suffer from the nucleophilic attack. [ABSTRACT FROM AUTHOR]