Transition‐metal‐catalyzed conjugated polymers of 1,6‐heptadiyne derivatives in supercritical carbon dioxide

Abstract

We investigated the polymerization of semifluorinated 1,6‐heptadiyne derivatives with MoCl5 as a catalyst in a supercritical carbon dioxide medium for the first time. The weight‐average molecular weight and polydispersity of the resulting polymers were in the ranges of 11.7–107.2 × 103 and 1.3–6.7, respectively. The 13C NMR spectrum of the polymers confirmed the five‐membered ring structure.

Synthesis of conjugated spirocyclic polymers: Cyclopolymerization of 1,1-dipropargyl-1-silacycloalkanes by transition metal catalysts

“…All procedures for the preparation of catalyst system and polymerization were carried out under dry nitrogen atmosphere because the active species are sensitive to moisture or oxygen [12]. Typical polymerization procedures are as follows.…”

“…A large variety of a,valkadiynes with different functionalities can be subject to the cyclopolymerization to yield a new type of conjugated polymer system [1,[18][19][20][21][22][23][24]. The resulting polyacetylenes with cyclic recurring units along the backbone display good long-term stability towards oxidation and good solubility in common organic solvents such as chlorobenzene, benzene, chloroform, and DMF [12,[25][26][27][28][29][30].…”

“…More manageable conjugated polymers have been prepared by the introduction of functional substituents into the polyacetylene. The substituents caused important changes in the properties of polymer, such as solubility, stability, melting, chemical, optical, electrical, and other properties [1,2,[9][10][11][12][13][14][15][16].…”

Electro-optical and electrochemical properties of an conjugated cyclopolymer: Poly(9,9-dipropargylfluorene)

“…Because of these properties, polyacetylene and its homologues have been promising as organic semiconductors, as membranes for gas separation and for liquid-mixture separation, as chirooptical materials, as side-chain liquid crystals, as materials for chemical sensors, and as materials for nonlinear optical property and for photoluminescence and electroluminescence properties [8][9][10][11][12][13][14][15].…”

Electro‐Optical and Electrochemical Properties of a Conjugated Polymer Prepared by the Cyclopolymerization of Diethyl Dipropargylmalonate

“…Thus it was difficult for practical applications to optoelectronic devices as an active material. Introduction of substituents at 4-position of 1,6-heptadiyne can enhance the processibility and stability of the polyene systems, thus a variety of substituted poly(1,6-heptadiyne)s were designed and synthesized [5,7,10,[18][19][20].…”