Acyclic diene metathesis

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Acyclic diene metathesis or 'ADMET' (distinguish from ADME) is a special type of olefin metathesis used to polymerize terminal dienes to polyenes:

ADMET ADMET general scheme.svg
ADMET

The new double bonds formed can be in cis- or trans-configurations. The exact ratio depends on the identities of the monomer and catalyst.

ADMET is a type of step-growth, condensation polymerization. It should be distinguished from ring-opening metathesis polymerization (ROMP), which is a chain-growth, addition polymerization. [1] Whereas ADMET is driven by the release of volatile ethylene gas, ROMP is driven by the relief of ring-strain.

While the concept of ADMET had been discussed in the scientific literature since the 1970s, the first successful ADMET polymerization was reported in 1991. [2] In this report, 1,5-hexadiene and 1,9-decadiene were polymerized to 1,4-polybutadiene and poly(octenylene), respectively. The polybutadiene had a weight average molar mass (Mw) of 28,000 with over 70% trans double bonds. The poly(octenylene) had an Mw of 108,000 with over 90% trans double bonds.

ADMET has been applied in the synthesis of a variety of polymers. Because of the higher degree of control in ADMET than in traditional radical polymerizations, it has been used to synthesize model polymers that would otherwise be difficult to prepare. Examples include purely linear polyethylene, alternating and block copolymers of ethylene with various other vinyl monomers, chiral polymers and polymers with embedded amino acids. [3] The high functional group tolerance of ruthenium-catalyzed ADMET has been applied in the synthesis of new supramolecular structures. [4]

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<span class="mw-page-title-main">Diene</span> Covalent compound that contains two double bonds

In organic chemistry, a diene ; also diolefin, dy-OH-lə-fin) or alkadiene) is a covalent compound that contains two double bonds, usually among carbon atoms. They thus contain two alkene units, with the standard prefix di of systematic nomenclature. As a subunit of more complex molecules, dienes occur in naturally occurring and synthetic chemicals and are used in organic synthesis. Conjugated dienes are widely used as monomers in the polymer industry. Polyunsaturated fats are of interest to nutrition.

<span class="mw-page-title-main">Petrochemical</span> Chemical product derived from petroleum

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<span class="mw-page-title-main">Poly(methacrylic acid)</span> Chemical compound

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References

  1. Mutlu, H.; Montero de Espinosa, L.; Meier, M.A.R. (2011). "Acyclic diene metathesis: a versatile tool for the construction of defined polymer architectures". Chemical Society Reviews. 40 (3): 1404–1445. doi:10.1039/B924852H.
  2. Wagener, K.B.; Boncella, J.M.; Nel, J.G. (1991). "Acyclic diene metathesis (ADMET) polymerization". Macromolecules. 24 (10): 2649–2657. Bibcode:1991MaMol..24.2649W. doi:10.1021/ma00010a001.
  3. Baughman, T.M.; Wagener, K.B. (2005). "Recent Advances in ADMET Polymerization". Advances in Polymer Science. 176: 1–42. doi:10.1007/b101318. ISBN   978-3-540-23358-9.
  4. Hou, H.; Leung, K.C.-F.; Lanari, D.; Nelson, A.; Stoddart, J.F.; Grubbs, R.H. (2006). "Template-Directed One-Step Synthesis of Cyclic Trimers by ADMET" (PDF). Journal of the American Chemical Society. 128 (48): 15358–15359. doi:10.1021/ja065572j. PMID   17131986.