1070-4272/04/7711-1835 2004 MAIK Nauka/Interperiodica Russian Journal of Applied Chemistry, Vol. 77, No. 11, 2004, pp. 1835 1839. Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 11, 2004, pp. 1853 1857. Original Russian Text Copyright 2004 by Zhubanov, Kravtsova, Mukhamedova. ORGANIC SYNTHESIS AND INDUSTRIAL ORGANIC CHEMISTRY Chlorinated Polyimides B. A. Zhubanov, V. D. Kravtsova, and R. F. Mukhamedova Bekturov Institute of Chemical Sciences, Ministry of Education and Science of the Kazakhstan Republic, Almaty, Kazakhstan Received March 19, 2004 Abstract Photoinitiated reaction of maleic anhydride with chlorobenzene and o-chlorotoluene in the pres- ence of a sensitizer (benzophenone) was studied with the aim to prepare chlorinated tricyclodecenetetracar- boxylic dianhydrides. New halogenated polyimides were prepared by the reactions of these products with various diamides in N-methyl-2-pyrrolidone in the presence of catalysts. The chemistry of halogenated macromolecular compounds is a specific field of the polymer chemis- try. It attracts researchers’ attention because these compounds exhibit specific, often unique properties; this makes them indispensable in the modern engi- neering, medicine, and other fields. A particular place among such compounds is occupied by polyimides (PIs). By now, the most studied are aromatic PIs. At the same time, certain studies show that alicyclic poly- imides are also promising thanks to a favorable com- bination of chemical, physicomechanical, dielectric, and other properties [1, 2]. Some recent papers are devoted to fluorinated PIs; data on chlorinated PIs are virtually lacking. The Diels Alder reaction occurring upon sensitized UV irradiation of solutions of maleic anhydride (MA) in aromatic hydrocarbons yielded the corresponding chlorinated dianhydrides: R R +2 C C = = O O O O C C = = O O R R C C = = O O O, h R R +2 C C = = O O O O C C = = O O R R C C = = O O O, h where R = H, Cl; R = H, CH 3 . In this work we studied the specific features of preparation of chlorinated dianhydrides and PIs de- rived from them. EXPERIMENTAL The starting compounds and solvents were purified by standard procedures. The IR spectra were recorded on an IR-25 spectrometer; samples of the monomers were prepared as KBr pellets, and samples of the polymers, as 3 5- m films. The 1 H NMR spectra were recorded on a Tesla BS-487B spectrometer in deuteroacetone (working frequency 80 MHz, internal reference hexamethyldisiloxane). The reduced viscosities of 0.5% solutions of PI were measured in an Ubbelohde viscometer at 25 C in DMSO. Thermogravimetric analysis of the poly- mers was performed on a TGA SDTA Metler Toledo device at a heating rate of 8 deg min 1 . The tempera- tures of the onset of polymer degradation, T o.d , were calculated from the TG curves. The physicomechanical (tensile strength, relative elongation) and dielectric (dielectric loss tangent, dielectric permittivity) characteristics were studied under standard conditions [3, 4]. The dianhydrides were prepared by the Diels Alder reaction upon irradiation of saturated solutions of MA in appropriate hydrocarbons in the presence of a sensi- tizer, benzophenone. 7-Chlorotricyclo[4.2.2.0 2,5 ]dec- 7-ene-3,4,9,10-tetracarboxylic dianhydride [adduct of chlorobenzene (CB) and MA, ACB] was prepared in a temperature-controlled quartz glass reactor upon irradiation of a solution of MA (225.41 g, 2.30 mol) in 1000 ml of CB, containing 45.53 g (0.25 mol) of benzophenone, with a PRK-2M mercury quartz lamp (375 W) for 25 h. In the course of irradiation, a color- less crystalline precipitate formed, which was filtered off, recrystallized from acetic anhydride, washed with anhydrous diethyl ether, and dried in a vacuum at 80 90 C to constant weight; yield of ACB based on MA 74.2%. 7-Chloro-8-methyltricyclo[4.2.2.0 2.5 ]dec-7-ene- 3,4,9,10-tetracarboxylic dianhydride [adduct of