Polymerization of Triazolinediones with trans-3,3-Dichloro-1-phenyl-1-propene

The reaction of 4-phenyl-1,2,4-triazoline-3,5-dione (PhTD) ( 2 ) with trans-3,3-dichloro-1-phenyl-1-propene ( 4 ) was investigated at room and reflux temperatures in methylene chloride solution. Although the reaction is slow, it gives quantitative yield. This reaction leads to the formation of two 2:1 adducts via double Diels–Alder and Diels–Alder-Ene reactions in a ratio of about 1: 7. The major product was isolated by means of fractional crystallization as a pure compound and was characterized by infra-red (IR), ¹H nuclear magnetic resonance (NMR), ¹³C NMR, mass spectra and elemental analysis. The structure of the minor product was determined by IR and ¹H NMR. These compounds were used as models for the polymerization reactions. The reaction of bistriazolinediones (1,6-bis-(3,5-dioxo-1,2,4-triazoline-4-yl)hexane and bis-(p-3,5-dioxo-1,2,4-triazoline-4-ylphenyl)methane) with ( 4 ) was carried out in dimethylformamide (DMF). The reactions gave novel polymers via repetitive double Diels–Alder and Diels–Alder-Ene polyaddition reactions, with the major component being a Diels–Alder-Ene structure. These polymers have intrinsic viscosities in a range from 0·08 to 0·18dlg^-1 in DMF. The physical properties and structural characterization of these polymers have been studied and are reported. © of SCI.