Synthesis of Biobased Polymers derived from Terpenes

Identifier:  TDX:2611

Handle: https://hdl.handle.net/20.500.11797/TDX2611

Authors:  Peña Carrodeguas, Leticia

Abstract:
Aminotriphenolate Al (III) and and Fe (III) complexes combined with a nucleophile have been investigated as binary catalytic systems for ROCOP reactions to afford perfectly alternating bio-renewables polymers. The coupling of limonene oxide and carbon dioxide to obtain polycarbonates has been studied. These catalysts are able to produce stereoregular trans configured polymers from cis limonene oxide. The Al (III) catalyst shows the potential to transform both stereoisomers of limonene oxide with high conversion levels under neat conditions. Furthermore, we synthesized six partially or fully renewable tricyclic anhydrides and copolymerized them with propylene oxide and cyclohexene oxide. By varying both the epoxide and the anhydride, we were able to increase the Tg of the resulting polymers over nearly 120 °C from 66 °C to an exceptionally high 184 °C. We have investigated the use of terpene derived epoxides (limonene oxide, carene oxide, limonene dioxide and menthene oxide) for the ROCOP in the presence of various aromatic anhydrides. These copolymerization reactions were performed using Fe(III) based aminotriphenolate complex and PPNCl providing partially bio-based semi-aromatic polyesters with glass transition temperatures spanning from 59 to 243 ºC. Finally, Al (III) aminotriphenolate and PPNCl were used for the preparation of a series of fatty acid derived biocarbonates. This catalyst system allows to convert the fatty acid derived epoxides maintaining high levels of diastereospecificity.