聚己內酯是生物可降解聚合物中重要的一員。由於其良好的生物相容性和易於熱塑性加工，它被廣泛用於醫療、食品和包裝材料。聚己內酯是極具未來潛力的化工商品，但現今市場上缺乏己內酯單體。本研究擬開發兩種製造己內酯的製程。第一種製程是由己二酸到己內酯的一步反應，所用的觸媒是釕-鉑-錫觸媒；第二種方法是以己二酸二甲酯為原料，先脫甲醇形成6-羥基己酸甲酯，再脫甲醇合環成己內酯，所用的觸媒是銅-錳-鋁和銅-鋅-鋁觸媒。使用釕-錫-鉑觸媒對己二酸進行加氫反應，會導致未知物的高選擇率。產生高選擇率的未知物可能是由於釕和錫的濃度以及反應溫度不夠高、使用低酸性擔體、高磁石攪拌速度，或是使用批次反應器使反應接觸時間過長導致寡聚物的產生。己二酸二甲酯在220℃和90 kg/cm2G下的氫解反應可以產生己內酯及6-羥基己酸甲酯，其脫甲醇後可通過閉環反應生產己內酯。在550℃下鍛燒的Cu:Mn:Al=42:15:2觸媒可用於生產高選擇率的6-羥基己酸甲酯。在400℃和300℃下鍛燒的Cu:Mn:Al=42:7:14觸媒可使己內酯的選擇率遠高於其他文獻。;Polycaprolactone (PCL) is an important member of biodegradable polymers. It is widely used in medical, food, and packaging materials due to its good biocompatibility and easy thermoplastic processing. Polycaprolactone is a chemical with great future potential, but it has a lack of caprolactone (CL) monomer in the market. This study intends to develop two processes for the formation of caprolactone. The first is a one-step reaction from adipic acid (ADA) to caprolactone, and the catalyst used is Ru-Pt-Sn. The second method is to use dimethyl adipate (DMA) as the raw material, first remove methanol to form methyl 6-hydroxyhexanoate (6-HHAME), and then remove methanol to form caprolactone by the cyclization reaction, and the catalysts used are Cu-Mn-Al and Cu-Zn-Al catalysts. The hydrogenation of adipic acid using Ru-Pt-Sn catalysts resulted in the high selectivity of unknown. The high selectivity of the unknown might be due to the concentration of ruthenium and tin and the reaction temperature not being high enough, the use of low acidic support, the high magnetic stirring speed, or the use of a batch reactor made the reaction contact time too long resulting in the formation of oligomers. The hydrogenolysis reaction of dimethyl adipate at 220℃ and 90 kg/cm2G can produce caprolactone and its precursor, methyl 6-hydroxyhexanoate. The catalyst of Cu:Mn:Al=42:15:2 calcined at 550℃ can be used to produce high selectivity of methyl 6-hydroxyhexanoate, which can be used to produce caprolactone by cyclization reaction after removing methanol. The catalysts of Cu:Mn:Al=42:7:14 calcined at 400℃ and 300℃ allow for a much higher selectivity of caprolactone than in other literature.
