ABSTRACT: A new methodology is described for the synthesis of poly(p-phenylenebutadiynylene)s based on the Pd/Cu-catalyzed, benzoquinone-mediated homocoupling of terminal acetylenes. Homopolymers synthesized from the 2,5-dialkoxy-1,4-diethynylbenzene monomers 1,4-bis(decyloxy)-2,5-diethynylbenzene and 1,4-bis(hexadecyloxy)-2,5-diethynylbenzene were largely insoluble, with the soluble portion from the polymerization of 1,4-bis(hexadecyloxy)-2,5-diethynylbenzene exhibiting a number-average molecular weight of 14,000. Completely soluble polymers were obtained from these precursors by the random copolymerization of these monomers. The materials exhibited number-average molecular weights ranging from 67,000 to over 150,000. The ultraviolet-visible and emission spectra of these polymers were examined and found to be very similar to those of structurally analogous poly(p-phenyleneethynylene)s and smaller poly(p-phenylenebutadiynylene)s reported by Kijima et al. (J Mat Chem, 1998, 8, 2165
