Partially biobased polymers: The synthesis of polysilylethers via dehydrocoupling catalyzed by an anionic iridium complex

Partially biobased polysilylethers (PSEs) are synthesized via dehydrocoupling polymerization catalyzed by an anionic iridium complex. Different types (AB type or AA and BB type) of monomers are suitable. Levulinic acid (LA) and succinic acid (SA) have been ranked within the top 10 chemicals derived from biomass. BB type monomers (diols) derived from LA and SA have been applied to the synthesis of PSEs. The polymerization reactions employ an air-stable anionic iridium complex bearing a functional bipyridonate ligand as catalyst. Moderate to high yields of polymers with number-average molecular weights (M-n) up to 4.38 x 10(4) were obtained. A possible catalytic cycle via an Ir-H species is presented. Based on the results of kinetic experiments, apparent activation energy of polymerization in the temperature range of 0-10 degrees C is about 38.6 kJ/mol. The PSEs synthesized from AA and BB type monomers possess good thermal stability (T-s = 418 degrees C to 437 degrees C) and low glass-transition temperature (T-g = -49.6 degrees C). (C) 2019 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.