HIGH TEMPERATURE POLYNAPHTHALENE NETWORKS

摘要

The Pd(0) catalyzed coupling of phenyl acetylene with aryl dibromide ditriflates affords bis-ortho-diynylarene (BODA) monomers in three high yielding steps from common bisphenols. Heating BODA monomers at 210 deg C in solution or neat results in controlled radical mediated step growth cyclopolymerization providing branched polynaphthalene oligomers containing reactive pendant and terminal aryldiynes. Polymerization is characterized by large melt widows (4-5h) at 210 deg C prior to vitrification. Oligomers ranging from 3000-24000 M_w with polydispersities (M_w/M_n) from 3-11 can be solution or melt coated or molded and thermally cured to 450 deg C without the formation of volatile products. Glass transition temperatures were not detected <400 deg C for the polynaphthalene networks and thermal stability ranging from 0.5-1.5 percent/hour weight loss was measured at 450 deg C in nitrogen. Heating to 900-1000 deg C gives glassy carbon solids in high yield. BODA monomer synthesis, network characterization arid kinetics, processability, and thermal properties are presented.