IS THE SYNTHESIS OF FULLY LINEAR UNBRANCHED poly-p-DIETHYNYLBENZENE POSSIBLE?
Abstract
The review reports on a set of specific properties inherent in polymers based on substituted acetylenes. Polymers synthesized from p-diethynylbenzene are of particular interest. Due to the presence of two reactive groups
–C≡C–H in the monomer, p-diethynylbenzene polymers, in principle, can be soluble or insoluble, while having one of three types of intramolecular structure: linear, branched, or crosslinked. It has been suggested that polymer clusters with heteroatoms along the main polymer chain can be obtained on the basis of linear poly-p-diethynylbenzene. Such clusters can be obtained by carrying out polymer-analogous transformations of the initial linear poly-p-diethynylbenzene due to the presence of –Ph–C≡C–H groups in each unit. Solid-phase, gas-phase, and liquid-phase methods of monomer polymerization under various conditions are considered. It has been shown that solid-phase polymerization leads to oligomeric, branched soluble and insoluble products. Gas-phase and liquid-phase polymerization in the melt lead to insoluble products. Liquid phase polymerization in the presence of various catalysts leads to branched soluble and insoluble polymers. Taking into account the results of the performed physicochemical studies for each publication, an assessment of the possible type of the realized intramolecular structure of the polymer was carried out; the properties of the synthesized polymers were given. It was shown that for the first time a linear polymer was synthesized in Russia in the presence of the anionic initiator n-butyllithium in the medium of hexamethylphosphoric triamide. The results of studies of the intramolecular structure of the homo- and copolymer of p-diethynylbenzene with diphenyldiacetylene are shown. Reactions of polymer-analogous transformations with “anionic” poly-p-diethynylbenzene were carried out. The publications are considered, in which possible areas of application of linear poly-p-diethynylbenzene are proposed, in particular: heat-resistant material; thin-film material for dry lithography; additives to industrial resins and oligoesteracrylates, which increase coke residue and stability at high operating temperatures; modifiers of carbon fiber materials. The results of the analysis of possible cis-trans isomers taking into account the attachment of units of the head-tail or head-head type are presented.
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