Polymerization of Acetylenes Containing Heptadecafluorononenyloxy Group and Polymer Properties

Polymerizations of two kinds of fluorine-containing aromatic disubstituted acetylenes, 1-[p-(heptadecafluorononenyloxy)phenyl]-2-phenylacetylene (p-C9F17ODPA) and 1-[p-(heptadecafluorononenyloxy)phenyl]-1-hexyne (p-C9F17OPH) were studied with groups 5 and 6 transition-metal catalysts. p-C9F17ODPA polymerized with TaCl5-Et3SiH catalyst to give a new polymer over 70 yield and its maximum intrinsic viscosity ([η]) was as high as 2.1 dl g−1. p-C9F17OPH polymerized with Ta and Nb catalysts, but yield and [η] of the polymer were lower. Poly(p-C9F17ODPA) and poly(p-C9F17OPH) were in the form of a yellow solid and white solid, and began to lose weight at 410°C and 270°C, respectively, which indicates high thermal stability. Both polymers had a main-chain structure consisted of alternating double bonds, and were completely soluble in some fluorine-containing solvents such as m-(CF3)2C6H4 and CCl2FCClF2. Poly(p-C9F17ODPA) formed a tough film by solution casting, and showed high PO2 value [4×10−8 cm3 (STP) cm cm−2 s−1 cm Hg−1] comparable to that of poly(dimethylsiloxane).