t-Butylacetylene was polymerized by MoC1 5 and WC16 as catalysts at 30oC or ooc in hydrocarbon and halogenated hydrocarbon solvents. Poly(t-butylacetylene) was obtained in high yield especially with MoC1 5 , and the highest polymer molecular weight exceeded 3 x 10 5 . The following relationship was obtained between the viscosity and molecular weight: [IJ]=I0-5 · 12 M/.Dl. The polymer was soluble in nonpolar solvents, particularly in aliphatic hydrocarbons. The infrared (IR), 1 H nuclear magnetic resonance (NMR), and 13 C NMR spectra supported the expected polymer structure, fCH=C(t-BuHn· A pair of doublets were observed for the methyl carbon in the 13 C NMR of polymer, making possible an evaluation of geometric structure.

SynopsisPolymerization of 1-chloro-2-phenylacetylene was effected by the catalyst formed by UV irradiation of MO(CO)~ in carbon tetrachloride to provide in high yield a polymer whose weight-average molecular weight reached 2 X lo6. UV irradiation and an appropriate halogenated hydrocarbon were essential for the formation of active species. The formation of a metal carbene as active species was inferred. Poly(1-chloro-2-phenylacetylene) was a light-yellow solid having the structure +CCl=CPh+,.The polymer was soluble in aromatic and halogenated hydrocarbons, and a film could be formed from polymer solution.

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The formation of complexes of soluble poly(phenylacetylene)s [poly(PA)s] with various electron acceptors [2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), 7, 7,8,8-tetracyano-pquinodimethane (TCNQ), bromine, trifluoromethanesulfonic acid, and antimony pentachloride] was studied spectrophotometrically. The complexes showed an absorption in the region from 700 to 940nm. The ratios of the polymer to DDQ and to bromine in the complexes were determined to be 3: I. The I: I mixtures of poly(PA) with DDQ and with TCNQ showed conductivities of ca. w-s ohm-1 cm-1 , whereas that of poly(PA) was as low as 10-14 -10-17 ohm-1 cm-1 . Then-type conduction was confirmed by thermoelectric-power measurement.