Polymerization of bis(3-trimethylsilyl-2-propynyl)ether and its copolymerization with diethyl dipropargylmalonate

Abstract

The polymerization of a cyclopolymerizable disubstituted dipropargyl ether, bis(3-trimethylsilyl-2-propynyl)ether (BTPE), was attempted by various transition metal catalysts. The yield for the polymerization of BTPE was generally low, which is possibly due to the steric hindrance of bulky substituents. In general, the catalytic activities of Mo-based catalysts were found to be greater than those of W-based catalysts. The highest yield was obtained when the MoCl 5 -EtAlCl 2 (1 : 2) catalyst system was used. The copolymerization of BTPE and diethyl dipropargylmalonate yielded a random copolymer with conjugated polymer backbone. However the polymers were partially desilylated, depending on the reaction conditions. The thermal and morphological properties of the resulting polymers were also discussed.

Functional polydiynes prepared by metathesis cyclopolymerization of 1,7-dihalogen-1,6-heptadiyne derivatives

“…S1, † the FTIR spectrum clearly indicates the presence of conjugated CuC bond (2240 cm −1 ) in M1 and the absence of the CuC bond in P1. This observation is supported by the analysis of 13 C NMR spectra (Fig. 1); two peaks appearing at 60.89 and 63.86 ppm in the spectrum of M1 assigned to the carbon atoms in CuC, which disappear completely in the spectrum of P1 and transformed into broader peaks over the range of 120-140 ppm, indicating the complete consumption of the triple bond and transformation into a double-bond after the polymerization reaction.…”

“…Fourier transform infrared (FTIR), 1 H NMR, 13 C NMR and UVvis spectroscopic techniques were employed to confirm the chemical structure of the resultant polymers. As demonstrated in Fig.…”

“…Generally, there are two routes to functional PDSAs, one is metathesis/insertion polymerization of disubstituted acetylenes and the other is metathesis cyclization polymerization of 1,7-disubstituted-1,6heptadiynes monomers. 6,7,[12][13][14][15][16][17][18][19] In recent years, metathesis cyclopolymerization (MCP) of diynes has been utilized as a powerful tool to prepare func-tional polyacetylenes (PAs). The PAs derived from MCP method demonstrated interesting electrical, optical, and magnetic properties, allowing them to be promising materials for various high-tech applications.…”

Electro-optical properties of poly(2-ethynyl-N-propargylpyridinium compound) with different counter ions

“…Especially, the substituted PAs have been prepared by the linear polymerization of the corresponding 1567 acetylene monomers by various catalyst systems [8][9][10][11][12][13][14][15][16][17][18][19]. The polymers having a conjugated backbone are expected to show unique properties such as electrical conductivity, paramagnetism, migration and transfer of energy, color, and chemical reactivity and complex formation ability [9].…”

“…Thus it was difficult for practical applications to opto-electronic devices as an active material. To overcome these problems of PA itself, various types of conjugated polymers including poly(aromatic heterocycle)s were prepared and characterized [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19].…”