| 摘要 |
Catalytic processes have been developed for direct chemical conversion of amides to methyl ether polymers or methyl ether ladder polymers. Amides formed by reacting acetic acid with monoethanol amine (MEA) or acetic acid with butylamine were polymerized in the presence of transition metal catalysts in air to form linear polymers. Ethanol acetamide was catalytically converted to a linear polyether as characterized by FTIR spectra. The catalysts were based on molecular strings of mono-, di- or tri-valent transition metal compounds that opened the amide carbonyl double bond to produce linear polyethers. Laboratory results have demonstrated [cobalt(II)]2, [manganese(II)]2, cobalt(II)-manganese(II), [nickel(II)]2 and related families of catalysts to be effective for formation of methyl ether polymers by this process. Similar transition metal catalysts plus hydrogen peroxide facilitated reactions of the amide compounds dimethylacetamide (DMAc), DMF as well as amides formed from L-cysteine with MEA, serine with MEA, arginine with MEA and histidine with MEA to form insoluble methyl ether ladder polymers at or near ambient temperature that were quite different from the linear polyether polymers. Catalysts active for these polymerizations were based on di- or tri-valent transition metals. The polymer formed from DMAc using a Co(III) catalyst plus 20% hydrogen peroxide was a ladder polymer as characterized by FTIR spectroscopy and isolated solids were observed to be microscopic hexagonal needle shaped crystals. The catalysts were based on molecular strings of tri-valent transition metal compounds. Laboratory results have demonstrated [cobalt(III)]2 and related families of catalysts in the presence of hydrogen peroxide to be effective for formation of methyl ether ladder polymers.
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