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An organic ester p-nitrobenzyl acetate (PNBA) was synthesized and used to establish a kind of autogenic acid system through the hydrolysis of ester to acetic acid in situ. The autogenic acid system can form a homogeneous solution by adding an organic solvent. The autogenic acid system possesses the desired characteristic in which hydrolysis can generate a small amount of acetic acid below 120 °C and a large amount of acid above 140 °C in 2 h. The acid-generated ability at different time and temperature was studied in detail. The dissoluti