Development of Prediction Models on Base-Catalyzed Hydrolysis Kinetics of Phthalate Esters with Density Functional Theory Calculation

摘要

Many phthalate esters (PAEs) are chemicals of high production volume and of toxicological concern. The second-order rate constant for base-catalyzed hydrolysis (k(B)) is a key parameter for assessing environmental persistence of PAEs. However, the k(B) values for most PAEs are lacking, and the experimental determination of k(B) encounters various difficulties. Herein, density functional theory (DFT) methods were selected by comparing empirical k(B) values of five PAEs and five carboxylic acid esters with the DFT-calculated ones. Results indicate that PAEs with cyclic side chains are more vulnerable to base-catalyzed hydrolysis than PAEs with linear alkyl side chains, followed by PAEs with branched alkyl side chains. By combining experimental and DFT-calculated second-order rate constants for base-catalyzed hydrolysis of one side chain in PAEs (k(B_side chain)), quantitative structure-activity relationship models were developed. The models can differentiate PAEs with the departure of the leaving group (or the nucleophilic attack of OH-) as the rate-determining step in the hydrolysis and estimate k(B) values, which provides a promising way to predict hydrolysis kinetics of PAEs. The half-lives of the investigated PAEs were calculated and vary from 0.001 h to 558 years (pH = 7 similar to 9), further illustrating the necessity of prediction models for hydrolysis kinetics in assessing the environmental persistence of chemicals.