Study On The Synthesis Of Bisphenols Containing Special Structure

Bisphenols are an important group of monomer of high polymer material including Makrolon PC, epoxy resin, polysulfone resin and so on. Using bisphenol compounds with special functional structure as monomers, polymer materials with good performance, such as heat resistance, flame retardant, optical properties, etc, were obtained. This article mainly studied the three bisphenol compounds with special structure:bisphenol compounds1,1-bis(4-hydroxyphenyl)cyclooctane with cyclooctyl moiety,9,9-dimethyl-9H-xanthenes-3,6-diol with xanthene moiety,4,4,4’,4’-tetramethyl-2,2’-spirobi-[chroman]-7,7’-diol with spirodichroman moiety. By the optimization of the synthesis conditions, it can get the best synthesis process conditions in order to further expanded production.(1) Study on the synthesis of1,1-bis(4-hydroxyphenyl)cyclooctane.1,1-bis (4-hydro-xyphenyl)cyclooctane was synthesized from cyclooctanone and phenol, using dried hydrogen chloride gas as catalyst,β-mercaptopropionic acid as cocatalyst, at room temperature and ordinary pressure. The chemical structure of1,1-bis(4-hydroxyphenyl)-cyclooctane was confirmed with1H NMR, MS and IR. The results show that hydrogen chloride gas is better than other acids, mercaptans/thiophenols are efficacious cocatalyst, heating is unfavourable for the reaction. The optimized reaction condition was n(cyclooctane): n(phenol):n(β-mercaptopropionic acid)=1:5:0.1, absence of solvent, react at room temperature and ordinary pressure under dried hydrogen chloride gas atmosphere for5days, and the yield was81.0%(HPLC).(2) Study on the synthesis of9,9-dimethyl-9H-xanthene-3,6-diol (compound A) and different ketone instead of acetone.9,9-dimethyl-9H-xanthene-3,6-diol was synthesized from acetone and resorcinol, using acid as catalyst, at high temperature and no solvents added. The optimized reaction condition was n(acetone)/n(resorcinol)=1:2.5, polyphosphoric acid10mol%as catalyst, absence of solvent, react at140℃for10h. The yield was93.2%(HPLC). Using the optimized reaction condition for the different ketones, butanone and diphenyl ketone got good results, and the yields were respectively79%and77%.(3) The optimization of reaction conditions of4,4,4’,4’-tetramethyl-2,2’-spirobi[chroman]-7,7’-diol(compound C). The starting material was still acetone and resorcinol, and the catalyst was respectively Amnerlyst-15resin and concentrated hydrochloric acid. The condensation reaction got taget compound by high yield in the toluene. The ratio of acetone and resorcinol was3:5:using Amberlyst-15resin as catalyst, the temperature was85℃and the reaction last6.5h; using concentrated hydrochloric acid as catalyst, the temperature was100℃and the reaction last5h. The yield of product C was respectively91.3%and85.7%(HPLC).And the flavan product can be transform to the spirodichroman product under the raction condition.