Mechanistic and synthetic studies aimed at the development of single-site metal alkoxide catalysts for the generation of polyesters and polycarbonates
The work proposed herein focuses on the chemistry of metal-oxygen bonds with respect to insertion/enchainment reactions involving epoxides, cyclic esters and carbonates, acid anhydrides and carbon dioxide leading to the formation of polyethers, polyesters and polycarbonates from renewable resources. Particular emphasis is placed on the use of the biologically benign metals magnesium and calcium and the M(3+) ions of aluminum, chromium and cobalt that have a similar ionic radii but different coordination properties arising from their respective d0, d3 and d6 valence shell configurations. The work emphasizes the design and use of single-site metal catalysis involving LMOR initiating and propagating species. For M = Mg and Ca, L is a pyrazolyl borate ligand specifically tailored to the coordination properties of the metal. In addition the ligand is inert with respect to reactions of the substrates under consideration. For the M(3+) ions, L is a substituted porphyrin, namely 5,10,15,20-tetraphenylporphyrin, TPP, 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, TFPP or 2,3,7,8,12,13,17,18-octaethylporphyrin, which together with Lewis base co-catalysts will allow the elucidation of factors leading to polyethers, polycarbonates and cyclic carbonates in reactions involving epoxides and CO2. Specific attention is given to reactions involving propylene oxide and styrene oxide which commonly show competitive formation of products. Electronic structure calculations employing Density Functional Theory will be carried out to elucidate the ring opening of the epoxide by alkylcarbonate and alkoxide ligands and the chain growth mechanism. Polymerization of lactide will be investigated using inexpensive solid supports and catalytic routes to cyclic esters are proposed wherein complexation to metal ions may allow chemical amplification of specific rings. With an understanding of mechanisms involving the reactions of M-OR bonds the development of single-site catalysis for the production of new generation polymers from chemicals derived from renewable resources such as CO2, lactide and succinic anhydride will advance rapidly.
- Research Organization:
- The Ohio State Univ., Columbus, OH (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- FG02-07ER15844
- OSTI ID:
- 1062560
- Report Number(s):
- DOE/07ER15844-FINAL
- Country of Publication:
- United States
- Language:
- English
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