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- ItemIron-Based Binary Catalytic System for the Valorization of CO2 into Biobased Cyclic Carbonates(Washington, DC : ACS Publ., 2016) Büttner, Hendrik; Grimmer, Christoph; Steinbauer, Johannes; Werner, ThomasThe atom economic conversion of epoxidized vegetable oils and fatty acid derivatives with CO2 into cyclic carbonates permits the synthesis of novel oleo compounds from renewable resources as well as the valorization of CO2 as a C1-building block. Organic phosphorus salts proved to be selective catalysts for this reaction. In a widespread screening 11 inexpensive and nontoxic iron salts were evaluated as cocatalysts to enhance the reaction rate. In the presence of 0.25 mol % iron chloride the selectivity and conversion were significantly improved. The reaction parameters were optimized under solvent-free conditions, and the scope and limitation were evaluated for 9 epoxidized fatty acid esters and 4 epoxidized vegetable oils. The biobased carbonates were isolated in excellent yields up to 95% and can be considered to be based on 100% CO2 in respect to carbon. This binary catalyst system features high efficiency and plain simplicity while valorizing CO2 into cyclic carbonates based on renewable feedstocks.
- ItemCopolymerization of CO2 and epoxides mediated by zinc organyls(London : RSC Publishing, 2018) Wulf, Christoph; Doering, Ulrike; Werner, ThomasHerein we report the copolymerization of CHO with CO2 in the presence of various zinc compounds R2Zn (R = Et, Bu, iPr, Cy and Ph). Several zinc organyls proved to be efficient catalysts for this reaction in the absence of water and co-catalyst. Notably, readily available Bu2Zn reached a TON up to 269 and an initial TOF up to 91 h-1. The effect of various parameters on the reaction outcome has been investigated. Poly(ether)carbonates with molecular weights up to 79.3 kg mol-1 and a CO2 content of up to 97% were obtained. Under standard reaction conditions (100 °C, 2.0 MPa, 16 h) the influence of commonly employed co-catalysts such as PPNCl and TBAB has been investigated in the presence of Et2Zn (0.5 mol%). The reaction of other epoxides (e.g. propylene and styrene oxide) under these conditions led to no significant conversion or to the formation of the respective cyclic carbonate as the main product.