SYNTHESIS OF ALTERNATING COPOLYMERS AND OPTICALLY ACTIVE POLYMERS VIA DIELS-ALDER AND ENE REACTIONS USING N-SUBSTITUTED TRIAZOLINEDIONES

The aim of the first part of this investigation was the selection of a suitable plasticizer for the development of a new elastomeric impression material system using bis-triazolinediones as crosslinking agents. Isoeugenol was selected for this study. It was converted to its methyl urethane derivative. In order to evaluate the reactivity of the methyl urethane derivative of isoeugenol with bis-triazoline-diones, two model compounds were prepared by reaction of 4-Ph and 4-Me-1,2,4-triazoline-3,5-diones with this compound. The products were formed by a successive two-step Diels-Alder-ene reaction. Their structures were determined by using ('1)H NMR, ('13)C NMR, IR and mass spectra.; The reaction between the methyl urethane of isoeugenol and bis-triazolinediones yielded alternating copolymers with Diels-Alder-ene repeating unit. These copolymers are soluble in polar solvents. Intrinsic viscosities of the new copolymers were measured in N,N-dimethylformamide, and were found to be in the range of 0.20 dl/g. The copolymer with R = diphenylmethane showed very high thermal stability.; The purpose of the second part of this research was to synthesize optically active polymers using N-chiral-triazolinediones via the ene reaction. Thus, optically active pure S-(-)-and R-(+)-4-((alpha)-methylbenzyl)-1,2,4-triazoline-3,5-diones were synthesized using optically pure amine by a series of chemical transformations. S-(-)CTD was found to be quite stable in solvents such as CH(,2)Cl(,2), toluene and acetone, and it decomposes slowly in solvents such as DMF, DMSO and THF. The pseudo first-order kinetics for such a decomposition were studied.; The ene reaction of S-(-)CTD with propylene was carried out in order to obtain a model compound for further use in the study of modification of polydienes. Bromination of this compound with a solution of Br(,2) in carbon tetrachloride furnished the desired dibromide adduct. An X-ray diffraction analysis of a single crystal of this compound was determined. The absolute configuration was found to be S, and intramolecular hydrogen bonding was observed.; 1,4- and 1,2-Polydienes were modified with S-(-)- and R-(+)CTDs. The resulting polymers are optically active. The intrinsic viscosities of the modified polymers at various percents of conversion were measured. The intrinsic viscosity decreases as percent conversion increases. This is due to intramolecular interaction. Evidence for intra- and intermolecular associations was given by X-ray analysis of the model compound as well as by IR spectroscopy.