A triazine-based porous organic polymer catalysed epoxide to cyclic carbonate conversion under ambient CO2 pressure.
A triazine-based porous organic polymer catalysed epoxide to cyclic carbonate conversion under ambient CO2 pressure.
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DOI：
10.1002/asia.201901277
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发表时间：
2020-04
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通讯作者：
Tanmoy Biswas;Arjun Halder;K. S. Paliwal;Antarip Mitra;Gouri Tudu;R. Banerjee;Venkataramanan Mahalingam
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作者：
Tanmoy Biswas;Arjun Halder;K. S. Paliwal;Antarip Mitra;Gouri Tudu;R. Banerjee;Venkataramanan Mahalingam
在这项工作中，我们已经实现了环氧化物到环状碳酸酯的转化，使用无金属的聚合物催化剂在环境CO2压力（1.02大气压）下，使用气球设置。以三聚氯氰（CYA-Cl）和邻联茴香胺（ANIS）为原料，在无水DMF中，N2气氛下，通过共沸法合成了含三嗪基聚合物（CYA-ANIS）。在聚合物中三嗪和胺官能团的存在导致在273 K下CO2的吸附高达7 cc/g。这启发了我们利用该聚合物在四丁基碘化铵（TBAI）作为助催化剂的存在下将一系列官能化的环氧化物转化为相应的环状碳酸酯，该产物具有广泛的应用，如锂离子电池溶剂，聚碳酸酯的前体，该催化剂对不同的一元和二元醇的转化都是有效的。在作为助催化剂的四丁基碘化铵TBAI的存在下，在大气压下将环氧化物转化成它们相应的环状碳酸酯。研究表明，环氧化物上带有吸电子基团（如CH_2Cl、缩水甘油醚等），与简单的烷烃链连接的环氧化物相比，显示出更好的转化率。该催化剂混合物能够保持其反应性长达五个循环而不丧失其活性。催化后表征清楚地支持催化剂的非均相和可回收性质。
In this work we have achieved epoxide to cyclic carbonate conversion using a metal-free polymeric catalyst under ambient CO2 pressure (1.02 atm) using a balloon setup. The triazine containing polymer (CYA-ANIS) was prepared from cyanuric chloride (CYA-Cl) and o-dianisidine (ANIS) in anhydrous DMF as solvent by refluxing under the N2 gas environment. The presence of triazine and amine functional groups in the polymer results in the adsorption of CO2 up to 7 cc/g at 273 K. This inspired us to utilize the polymer for the conversion of a series of functionalised epoxides into their corresponding cyclic carbonates in the presence of tetrabutyl ammonium iodide (TBAI) as co-catalyst.The product has wide range of applications like solvent in lithium ion battery, precursor for polycarbonate, etc. The catalyst was efficient for the conversion of different mono and di-epoxides into their corresponding cyclic carbonates under atmospheric pressure in the presence of tetrabutyl ammonium iodide TBAI as co-catalyst. The study indicates that epoxide attached with electron withdrawing groups (like, CH2Cl, glycidyl ether, etc.) displayed better conversion compared to simple alkane chain attached epoxides. This catalyst mixture was capable to maintain its reactivity up to five cycles without losing its activity. Post catalytic characterization clearly supports the heterogeneous and recyclable nature of the catalyst.