In this review, all available publications on the polymerization of all isomers of bifunctional diethynylarenes due to the opening of C≡C bonds were considered and analyzed. It has been shown that with the use of polymers of diethynylbenzene, heat-resistant and ablative materials, catalysts, sorbents, humidity sensors, and other materials can be obtained. Various catalytic systems and conditions of polymer synthesis are considered. For the convenience of comparison, the publications considered are grouped according to common features, including the types of initiating systems. Critical consideration is given to the features of the intramolecular structure of the synthesized polymers since it determines the entire complex of properties of this material and subsequent materials. Branched and/or insoluble polymers are formed as a result of solid-phase and liquid-phase homopolymerization. It is shown that the synthesis of a completely linear polymer was carried out for the first time by anionic polymerization. The review considers in sufficient detail publications from hard-to-reach sources, as well as publications that required a more thorough critical examination. The review does not consider the polymerization of diethynylarenes with substituted aromatic rings because of their steric restrictions; the diethynylarenes copolymers with complex intramolecular structure; and diethynylarenes polymers obtained by oxidative polycondensation.
Keywords: anionic polymerization; catalytic activity; click reaction; intramolecular structure; liquid-phase polymerization; modification; poly-p-diethynylbenzene; solid-phase polymerization; stereoisomers.