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Polymeric aluminum porphyrin:Controllable synthesis of ultra-low molecular weight CO_(2)-based polyols

中国化学快报:英文版 2023年第8期34卷 434-438页

作者： Chunwei Zhuo Han Cao Xiaoshen Wang Shunjie Liu Xianhong Wang Key Laboratory of Polymer Ecomaterials Changchun Institute of Applied ChemistryChinese Academy of SciencesChangchun 130022China University of Science and Technology of China Hefei 230026China

Carbon dioxide-based polyols with ultra-low molecular weight(ULMW,Mn<1000 g/mol)are emergent polyurethane precursors with economic and environmental ***,the lack of effective proton-tolerant catalytic systems limits t... 详细信息

Carbon dioxide-based polyols with ultra-low molecular weight(ULMW,Mnaluminum porphyrin catalyst(PAPC)system was applied to the copolymerization of CO_(2)and propylene oxide,where sebacic acid,bisphenol A,poly(ethylene glycol),and water were used as chain transfer agents to achieve the controlled synthesis of CO_(2)-*** molecular weight of the resulting CO_(2)-polyols could be facilely regulated in the range of 400–930 g/mol at low catalyst loadings,fully demonstrating its catalytic advantages of high activity,high product selectivity,and excellent proton tolerance of ***,the catalytic efficiency of PAPC could reach up to 2.1–5.2 kg/g under organic CTA conditions,even reaching 1.9 kg/g using water as the *** cPC content could be controlled within 1.0 wt%under the optimized conditions,indicating the excellent controllability of the PAPC *** CO_(2)-polyols combines the advantages of low viscosity(∼3000 mPa s at 25°C),low glass transition temperature(∼−73°C),and high carbonate unit content(∼40%),which is important for the development of high-performance polyurethanes.

关键词： CO_(2)-polyols Polymeric catalyst aluminum porphyrin Ultra-low molecular weight Proton tolerance

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Temperature-responsive Catalyst for the Coupling Reaction of Carbon Dioxide and Propylene Oxide

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Chinese Journal of Chemistry 2018年第4期36卷 299-305页

作者： ChunweiZhuo Yusheng Qin Xianhong Wang Fosong Wang Key Laboratory of Polymer Ecomaterials Changchun Institute of Applied Chemistry Chinese Academy of Sciences Changchun Jilin 130022 China University of Science and Technology of China Hefei Anhui 230026China

The selective synthesis of polypropylene carbonate （PPC） and cyclic propylene carbonate （CPC） from coupling reaction of CO_2 and propylene oxide （PO） is a long term pursuing target. Here we report that a temperature controllable porphyrin aluminum catalyst using 5,10,15,20-tetra（1,2,3,4,5,6, 7,8-octahydro-1,4：5,8-dimethanoanthracen-g-yl）porphyrin as ligand, once in conjunction with suitable onium salt, achieved single cycloaddition or co- polymerization reaction. Only cydoaddition reaction happened at temperature above 75 ℃ to produce 100% CPC, whereas copolymerization became dominant to afford PPC with selectivity over 99% at 25℃, and the obtained PPC showed over 99% carbonate linkage and 92% head-to-tail structure. Based on systematic analysis of the electronic and steric feature in the porphyrin ligand, it was found that the electronic feature of the substituent in porphyrin ligand was decisive for PPC selectivity, porphyrin ligand bearing strong electron-donating substituents displayed a significantly reduced toler- ance towards increased temperature with respect to PPC formation. Therefore, temperature-responsive catalyst could be designed by suitable modifica- tion in porphyrin ligand, and such accurate synthesis of target product by one catalyst may create a useful and facile platform for selective PPC or CPC production.

关键词： carbon dioxide propylene oxide copolymerization cycloaddition aluminum porphyrin

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