Kinetics of the anionic polymerization of phenylacetylene

Anionic Polymerization of Para-Diethynylbenzene: Synthesis of a Strictly Linear Polymer

“…Interestingly, a weak band of 2190 cm −1 was detected in the IR spectrum of polymers, which is characteristic of the valence oscillation of the di-substituted bond –C≡C–. The appearance of this band could be explained by the fact that the chain is transferred to the monomer during polymerization, as was observed in the case of the polymerization of phenylacetylene ( Scheme 1 ) [ 31 ]. At the same time, the H ar+ol /H eth ratio should increase, which was observed in reality.…”

“…The lateral phenylene-ethynyl carbanion ~CH=C(Ph–C≡C − Li + )~ formed during the chain transfer reaction to the polymer is similar in structure and identical in properties to lithium phenylacetylide Ph–C≡C − Li + . It is known that lithium phenylacetylide is capable of initiating polymerization under these conditions [ 25 , 31 ]. These facts indicate the possibility of a chain transfer reaction to the polymer according to Scheme 2 .…”

Progress in the chemistry of polyconjugated systems

“…The following examples are typical of polymerization processes giving rise to PCSs: polymerizations of acetylene and diphenylacetylene 36-4D catalyzed by a system of ionic coordination type obtained by reacting vanadium acetylacetonate with Et3AI (cf.38)), thermal and radiation polymerization of propynoic acid and its salts4O, 41 --45), free ionic polymerization of phenylacetylene [46][47][48], and, finally, the polymerization of NN-dimethyl-2-propynylamine by the opening of the C=C-bond and simultaneous donor-acceptor interaction of the amino function with organic electron acceptors 49). The specific features of these processes will be treated in the following chapters.…”