The method for preparation of 3, 3' ,4, 4'-diphenyloxide tetracarboxylic dianhydride belongs to the organic synthetic field. The purpose of this invention is to provide a method for preparation of 3, 3' ,4, 4'-diphenyloxide tetracarboxylic dianhydride, in which its preparation technology is simlple, process flow is short, cost is low, three wastesquantity is few, and its solvents can be retrieved and reused and its products can be easily purified. It includes the following steps: produing the corresponding 4-halogenated potassium phthalate or natrium phthalate by the reaction between 4-halogenated benzoic anhydride and caustic potash or caustic soda; condensing the product of the former step and 4-halogenated benzoic anhydride in the non-polar solvent of dichlorobenzene or trichlorobenzene with organophosphorus compound and/or copper compound as its phase transfer catalyst to obtain monoether anhydride; hydrolyzing the obtained monoether anhydride in the organic acid to prepare monoether acid, afterwards, and closing loop and dehydrating them in the miscible liquids of ethyl acetate and acetic anhydride to prepare purified monoether anhydride. The method for preparation of monoether anhydride can easily control reaction conditions, and is of good stability, especially, is of no strict demand for water. |