T. Vahlenkamp et G. Wegner, POLY(2,5-DIALKOXY-P-PHENYLENE)S - SYNTHESIS AND PROPERTIES, Macromolecular chemistry and physics, 195(6), 1994, pp. 1933-1952
The synthesis of poly(2,5-dialkoxy-p-phenylene)s (PPP) by palladium-ca
talyzed polycondensation of 2,5-dialkoxy-4-bromophenylboronic acids is
described. Number-average degrees of polymerization of ca. 30 have be
en reached at best. The characterization of the polymers by NMR, IR, U
V-VIS and fluorescence spectra, data on the bulk structure obtained by
X-my methods, melting behavior and thermal stability are reported. PP
P's with long alkoxy side chains exhibit a layered phase structure, th
ose with short or branched alkoxy side chains, cylindrical packing. Po
ly(2,5-dibutoxy-p-phenylene) was prepared with chain lengths 7 less-th
an-or-equal-to P(n) less-than-or-equal-to 30. The polymer with P(n) of
30 shows thermal transitions in the bulk phase at 182-degrees-C and 2
27-degrees-C. It forms an anisotropic melt above 227-degrees-C which o
nly starts decomposing if heated above 300-degrees-C. The polymers of
shorter chain length show isotropic melts, with the melting point stro
ngly depending on chain length.