Polymerization of Phenylacetylenes. III. Structure and Properties of Poly(phenylacetylene)s Obtained by WCL₆ or MoCl₅

Abstract

Structure and properties of poly(phenylacetylene)s were investigated. The poly(phenylacetylene)s were obtained in the polymerization at 30°b y WCle or M0CI5 in several solvents (C6He, CCI4, CHCI3, and CH2CI2). Molecular weights of the polymers were 5500-12000. The polymers produced by WCle in polar solvents showed high softening points (~226°), a small absorption at 870 cm-1 in ir spectrum, and an emission at 430 nm by excitation at 250 nm; these were correlated with high content of trans structure. On the other hand, the polymers formed by M0CI5 in nonpolar solvents showed low softening points (~215°), a large absorption at 870 cm-1, and an emission at 360 nm, which were attributed to high content of cis structure. The numbers of unpaired spin of the polymers were in a range of 1016-1017 spin g_1, and the electric conductivities were 10"18-10"15 ohm"1 cm"1.

Polymerization of Phenylacetylenes. IX. Polymerization of β-Naphthylacetylene by WCl6 and MoCl5

“…11 In accordance with this, the absorption of poly(f:iNA) in the visible region is large and shows a red shift (see Figure 2), compared with that of poly(PA). 11 The softening points of polymers produced with…”

“…The polymerizations were performed as described before. 11 The IR, UV-visible, and electron spin resonance (ESR) spectra of polymers were obtserved as described in a previous paper.11 The X-ray powder diffraction patterns were obtained using a Shimadzu GX-3B. Differential thermal analysis (DTA) was performed on a Shimadzu-20B analyzer under nitrogen at a heating rate of l 0°Cjmin.…”

Mixed substituent poly[(vinyloxy)cyclotriphosphazenes]

“…The above observations indicate that the thermal decomposition processes for these polymers may have additional complexities, such as non-chain scission processes, beyond the previously proposed 13 model. An examination of the IR spectrum of the brittle black material remaining from the decomposition of 4 at 180 for one hour reveals a strong absorption band at 1634 cm À1 which is typical of a polyactylene fragment 22,23 which could arise from a 1,2 elimination reaction. The sample also showed single ESR resonance suggesting the possibility of trapping of a radical species in the decomposition process which is matrix stabilized even though the heating was in air.…”

Polymerization of (o-Phenylphenyl)acetylene and (2,5-Di-tert-butylphenyl)-acetylene and Polymer Properties

“…The methanol-soluble products formed with W and Mo catalysts consisted of linear oligomers and cyclotrimers, while those with Nb and Ta catalysts were mostly cyclotrimers. In the polymerization of phenylacetylene, the poly- 8 and is null ( cyclotrimers are selectively formed) with Nb and Ta catalysts. 9 Therefore it is interesting that introduction of a very bulky phenyl group onto the ortho position does not render the phenylacetylene unreactive but forms a polymer in sufficiently high yields.…”