Synthesis of new heterochain polyamines by reaction of diamines with diacetylene

Abstract

A STVDY of the reaction of diacetylene and amines in order to obtain monomeric addition products has been previously described [1]. Continuing the investigation of the reaction of diacetylene with diamines we found that they form in equimolar ratios heterochain polyamines, containing conjugated diene-amine groups [2]. A study is made in this paper of the reaction of diacetylene with primary and secondary alkylene diamines of the aliphatic and cyclic series and with diamines containing polyester groups and multiple bonds: with 1,6-diaminohexane, 1,4-diaminobutane, 1,2-diaminopropane, 1,2-diaminoethane, the di(~-aminopropyl)ester of diethylene glycol, triethylene glycol and 1,3-butylene glycol and other diamines. New types of polyamines I -VI t were obtained. Polymerization was carried out in bulk and in benzene solution (20% wt.) at 20 ° for three days in nitrogen. The reaction is exothermal. The yield of polymers I, I I and I I I was quantitative in practice. Polyamines V and VI are formed with yields of 40 to 70%. Aliphatic saturated secondary diamines react with diacetylene in several ways and the yield of polymer IV is 3-10% in all. A mixture of liquid products of the addition of a diamines to diacetylene of both acyclic and cyclic structure is mainly formed, the study of which continues. Steric factors, the possibility of screening of I~H-and C C H groups by alkyl radicals are evidently of significance in the reaction ofdiacetylenes with diamines, which is observed in constructing Stuart-Brigleb models. According to elementary analysis, the polyamines contain equimolar proportions of the initial monomers. The IR spectra of polyamines (Fig. 1) are in agreement with the main unit structure of the polymer described. The following absorption bands are typical: 1625-1580 cm -1 (conjugated diene group), ; 400-3200 cm -1 (amino-group) and for polyaminoesters--1120 cm -1 (ether groups). The IR spectra of polyamine frac-