| 摘要: | 中孔洞矽材具有高比表面積、適當孔洞大小與熱穩定佳等等的優勢，因此本 研究主要以中孔洞矽材做為底材，並修飾磺酸官能基，應用於酯化反應與佩希 曼縮合反應 (Pechmann Condensation)中。
本研究分成兩個部份。第一部份，本研究利用直接合成法，將磺酸官能基修 飾在中孔洞矽材 SBA-15 上。透過調整磺酸官能基與 TEOS 的比例，可合成出 一系列 S15SX (X = 5, 10, 20, 25, 30)的樣品。經過 SAXRD, BET, XPS, TGA 等儀 器鑑定確認材料結構的正確性與穩定性後，應用於三羥甲基丙烷 (TMP)酯化反 應，並分別探討不同結構中孔洞矽材、磺酸官能基比例、不同丙烯酸與三羥甲 基丙烷比例、不同溶劑比例、不同催化劑量等變因帶給反應的差異性。最後得 知 AA 與 TMP 的莫爾比 2:1、環己烷與甲苯的體積比為 2:1 時，加入 1.8g S15S10 並施以 25 c.c/min 的空氣流速，能達到 50 %TMPDA 產量。而且，回收測試實 驗中，當 S15S10 進行五次回收實驗後，仍具有 13%的 TMPDA 產量。
第二部份，本研究以擴孔的 SBA-16，LP-SBA-16 作為底材，並調整磺酸官能 基比例合成一系列樣品:LP-S16SX (X= 5, 10, 20)，應用於佩希曼縮合反應中。研 究中探討不同反應物比例、不同溫度、不同催化劑量、不同磺酸官能基比例以 及不同結構的催化劑所帶來的影響。最後，當 Resorcinol 與 EAA 的莫爾比例為 1:1.5、反應時間 5 分鐘、溫度為 130 °C 時，可達到 TOF 值為 810 (h-1)的效果。 在回收測試中，催化劑反應五次後仍具有 7%的產率。;In this study, we adapted silica mesoporous materials loading with sulfonic acid group as catalyst due to its high specific surface area, proper pore size and high thermal stability properties. During the first part, we synthesized S15SX (X = 5, 10, 20, 25, 30) with TEOS as the silicon source, MPTMS as the sulfonica acid group precursor and P123 as the soft template. Due to the BET results, S15S10 possess 555cm2/g high specific surface area and 1.01nm optimal pore size. Those properties seem to favor the performance in esterification. Therefore, we applied it into Fischer esterification to produce TMPDA and explored the best experimental condition. Finally, we found that adding 1.8g S15S10 and 25 c.c/min air flow in the solution when molar ratio of AA:TMP is 2:1 and volume ratio of cyclohexane:toluene is 2:1 could reach 50% TMPDA GC Percent. Moreover, S15S10 still could produce 13% TMPDA GC Percent after 5 times recycling test.
In the second part, we employed LP-SBA-16 as the supporting materials and loaded with different amount of sulfonic acid group (LP-S16SX, X = 5, 10 ,20). Its high specific surface area, optimal pore size properties may be possibly favor the Pechmann condensation. Eventually, we found that LP-S16S5 exhibited high performance (810 (h-1)) in Pechmann condensation at 130 °C. Last but not least, LP- S16S5 still could get 7 % yield after 5 recycling tests. |
