Pressure-induced polymerization of carbon monoxide: disproportionation and synthesis of an energetic lactonic polymer

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We have studied pressure-induced chemical reactions in carbon monoxide using both a diamond-anvil cell and a modified large volume press. Our spectroscopic data reveal that carbon monoxide disproportionates into molecular CO{sub 2} and a solid lactone-type polymer; photochemically above 3.2 GPa, thermochemically above 5 GPa at 300K, or at 3 GPa and {approx}2000K as achieved by laser heating. The solid product can be recovered at ambient conditions with a high degree of conversion, measured to be up to 95% of the original CO. Its fundamental chemical structure includes {beta}-lactone and conjugated C=C, which can be considered a severely modified polymeric ... continued below

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Evans, W J; Lipp, M J; Yoo, C; Herberg, J L; Maxwell, R S & Nicol, M F October 4, 2005.

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We have studied pressure-induced chemical reactions in carbon monoxide using both a diamond-anvil cell and a modified large volume press. Our spectroscopic data reveal that carbon monoxide disproportionates into molecular CO{sub 2} and a solid lactone-type polymer; photochemically above 3.2 GPa, thermochemically above 5 GPa at 300K, or at 3 GPa and {approx}2000K as achieved by laser heating. The solid product can be recovered at ambient conditions with a high degree of conversion, measured to be up to 95% of the original CO. Its fundamental chemical structure includes {beta}-lactone and conjugated C=C, which can be considered a severely modified polymeric carbon suboxide with open ladders and smaller five-membered rings. The polymer is metastable at ambient conditions, spontaneously liberating CO{sub 2} gases exothermically. We find that the recovered polymer has a high energy density, 1-8 KJ/g, and is very combustible. We estimate the density of recovered CO polymer to be at least 1.65 g/cm cm{sup 3}.

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  • Journal Name: Chemistry of Materials; Journal Volume: 18; Journal Issue: 10

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  • Report No.: UCRL-JRNL-215950
  • Grant Number: W-7405-ENG-48
  • Office of Scientific & Technical Information Report Number: 884767
  • Archival Resource Key: ark:/67531/metadc892676

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  • October 4, 2005

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  • Sept. 23, 2016, 2:42 p.m.

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  • Nov. 30, 2016, 6:10 p.m.

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Evans, W J; Lipp, M J; Yoo, C; Herberg, J L; Maxwell, R S & Nicol, M F. Pressure-induced polymerization of carbon monoxide: disproportionation and synthesis of an energetic lactonic polymer, article, October 4, 2005; Livermore, California. (digital.library.unt.edu/ark:/67531/metadc892676/: accessed October 18, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.