KI-醚类催化剂催化二氧化碳和环氧乙烷合成碳酸乙烯酯反应研究

Research on the KI Ether Catalysts for the Reaction of Carbon Dioxide with Oxirane to Ethylene Carbonate

合成了５个含有金属铁的环醚Ｆｅ（ＣＯ）３Ｌ（Ｌ１＝Ｐｈ２Ｐ（ＣＨ２ＣＨ２Ｏ）２ＣＨ２ＣＨ２ＰＰｈ２，Ｌ２＝Ｐｈ２Ｐ（ＣＨ２ＣＨ２Ｏ）４ＣＨ２ＣＨ２ＰＰｈ２，Ｌ３＝ＯＰｈ［（ＯＣＨ２ＣＨ２）ＰＰｈ２］２，Ｌ４＝ＯＰｈ［ＯＣＨ２ＣＨ２）２ＰＰｈ２］２）和［Ｆｅ（ＣＯ３）］２Ｌ５（Ｌ５＝［Ｐｈ２ＰＣＨ２ＣＨ２ＯＣＨ２ＣＨ２ＰＰｈ２］２）．对它们进行了元素分析，并用红外光谱和核磁共振谱进行了结构表征．用ＫＩ＋醚类为催化剂，催化二氧化碳与环氧乙烷反应生成碳酸乙烯酯，反应选择性大于９６．９％．催化机理为碱催化，催化剂的活性受醚的影响．能和Ｋ＋形成稳定配合物的醚可提高催化剂的活性．含金属铁的环醚和普通醚类相似，可以和钾离子作用，提高阴离子的亲核催化性能．

Five cycloether compounds containing metal Fe(CO) 3L, (L 1=Ph 2P(CH 2CH 2O) 2·CH 2CH 2PPh 2, L 2=Ph 2P(CH 2CH 2O) 4CH 2CH 2PPh 2, L 3=OPh[(OCH 2CH 2)PPh 2] 2, L 4=OPh[OCH 2CH 2) 2PPh 2] 2) and [Fe(CO 3)] 2L 5(L 5=[Ph 2PCH 2CH 2OCH 2CH 2PPh 2] 2) were synthesized. The composition of these compounds were determined and their structure were characterized with IR and P NMR. KI+ether was used as catalyst for reaction of carbon dioxide with oxriane to produce ethylene carbonate. The ether, which forms stable complex with K +,enhances the activity of KI. The cycloether compounds containing metal can react with K + ion and increase the nucleophilic reactivity of anion similar with ordinary ethers.