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July 29, 2021
from Osaka City University
By combining a CeO2 catalyst with atmospheric carbon dioxide, researchers from Osaka City University, Tohoku University and Nippon Steel Corporation have developed an effective catalytic process for the direct synthesis of polycarbonate diols without the use of dehydrating agents. Their method, published in Green Chemistry, is not based on toxic chemical raw materials such as phosgene and carbon monoxide, making it the world’s first « green » reaction system with high yields.
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There is a global need to reduce carbon dioxide, one of the major greenhouse gases, and its conversion into a useful chemical compound has received a lot of attention in recent years. Various effective catalyst systems have been developed, but they rely on toxic chemicals that produce uncontrollable by-products. As an alternative, processes have emerged that use readily available and safe substrates with water as the only by-product. However, high levels of water by-product prevent these processes from synthesizing enough polycarbonates.
« Most processes use a dehydrator to keep the water level low in order to overcome an equilibrium, » said Masazumi Tamura of Osaka City University, « But some of the problems to be solved are the high pressure of carbon dioxide that is required, the recovery and regeneration of the dehydrating agent, and contamination of by-products that arise from its use. »
To circumvent these problems, developed the research team used a catalytic process that does not use a dehydrating agent. By focusing on the difference in boiling points between the chemical product / diol and water, the research team predicted a high carbon fixation yield by blowing in CO2 at atmospheric pressure to evaporate excess water.
« It became clear that among those we were using Metal oxide catalysts, « said Keiichi Tomishige of Tohoku University, » CeO2 showed the highest activity. This simple catalytic reaction system is the first to successfully synthesize polycarbonate diols from carbon dioxide and diols at atmospheric pressure. « This process can chemically convert carbon dioxide without the need for dehydrating agents by using any substrate with a sufficiently higher boiling point than water, » concluded Kenji Nakao of Nippon Steel Corporation, « and can be applied to the synthesis of carbonates, carbamates, and ureas, which are useful additives for lithium-ion batteries and / or raw materials for polymer synthesis. »
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