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研究生:李彥君
研究生(外文):Yen-Chun Lee
論文名稱:釕金屬烯烴複分解催化試劑清除劑之設計與合成
論文名稱(外文):Synthesis and Design of Ruthenium-Based Olefin Metathesis Catalysts Scavenger
指導教授:林渝亞
指導教授(外文):Yu-Ya Lin
學位類別:碩士
校院名稱:國立中山大學
系所名稱:化學系研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2018
畢業學年度:106
語文別:中文
論文頁數:83
中文關鍵詞:二氧化矽奈米粒子金屬清除劑烯烴複分解
外文關鍵詞:metal scavengersilica nanoparticleolefin metathesis
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格拉布催化劑(Grubbs Catalyst)是目前最被廣泛應用的烯烴複分解(Olefin metathesis)催化試劑。在烯烴複分解反應中,開環複分解(Ring-opening metathesis,ROM)以及閉環複分解(Ring-closing metathesis,RCM)互為彼此的逆反應,因此在進行以上反應時,一旦反應時間過長,可能會導致試劑催化造成逆反應的發生,或是寡聚物的生成,而造成產率不理想。金屬清除劑的使用則可以在適當的時機使催化試劑失去活性,並且對於後續的純化有所助益。
本論文設計在二氧化矽之奈米粒子上修飾含硫醚官能基之末端烯烴作為金屬清除劑。利用硫原子和烯烴對催化劑中的釕金屬進行配位,生成穩定的環狀中間體,因此能阻斷催化劑繼續作用。而修飾在二氧化矽奈米粒子上則具有單位表面積大、可用離心方式分離等優點。
本論文中會探討鹼、反應時間對粒子大小的影響,以及開發方法並將其應用於分析單位重量之奈米粒子上所含烯烴官能基數量,其分別為使用兒茶酚硼烷(catecholborane)對烯烴進行硼氫化以及利用Ellman’s test對粒子進行二次分析,最後會探討其對於釕金屬催化劑的清除效果。
Grubbs catalyst is one of the most widely used olefin metathesis catalysts. Since ring-opening metathesis(ROM)and ring-closing metathesis(RCM)are the reverse reaction of each other, if the reaction was left for too long, the undesired reverse reaction may occur. In other cases, oligomers may be formed causing the low yield.
Metal scavengers can deactivate the catalyst at the right time and can be useful for subsequent purification. In this thesis, silica nanoparticles modified with terminal olefins containing thioether functional groups were investigated as potential scavenger for ruthenium-based metathesis catalysts. We envision that the coordination of the chalcogens and olefins with the ruthenium metal in the catalyst would form a stable cyclic intermediate, which results in the poisoning of the catalyst. The used of modified nanoparticle has the advantages of having larger surface area and ease of separation by centrifugation.
The effect of the amount of base and reaction time on particle diameter will be discussed. In addition, the method will be discussed to detectmine the quantity of olefinic functional groups modified on nanoparticles per unit weight. These include the hydroboration with catecholborane, and the indirect analysis of the particles using Ellman''s test. Finally, we will discuss the removal efficiency of the ruthenium metal catalyst.
論文審定書.................................................................................................................................i
公開授權書................................................................................................................................ii
謝誌...........................................................................................................................................iii
中文摘要....................................................................................................................................v
Abstract .....................................................................................................................................vi
目次..........................................................................................................................................vii
圖目錄.......................................................................................................................................ix
表目錄.......................................................................................................................................xi
光譜目錄..................................................................................................................................xii
縮寫表..................................................................................................................................... xiii
第一章 緒論............................................................................................................................. 1
1.1 研究背景.................................................................................................................. 1
1.1-1 烯烴複分解簡介..................................................................................................... 1
1.1-2 釕金屬烯烴複分解催化試劑................................................................................. 3
1.1-3 烯烴複分解反應機制............................................................................................. 4
1.1-4 烯烴複分解反應類型............................................................................................. 5
1.1-5 烯烴複分解在製藥產業的應用............................................................................. 6
1.2 釕金屬催化試劑的移除.......................................................................................... 8
1.2-1 簡單過濾與色譜方法............................................................................................. 9
1.2-2 進行均相官能化或清除釕物質後純化............................................................... 10
1.2-3 利用修飾在固相載體上的螯合基團進行純化................................................... 14
1.2-4 清除劑設計之概念............................................................................................... 19
1.3 奈米二氧化矽粒子................................................................................................ 20
1.3-1 製備奈米二氧化矽之方法概述........................................................................... 20
viii
1.3-2 溶膠-凝膠法 ......................................................................................................... 21
1.4 烯丙基氧族元素對烯烴複分解之影響................................................................ 22
1.4-1 烯丙氧的活化效應............................................................................................... 22
1.4-2 烯丙硫元素對複分解的影響............................................................................... 24
第二章 研究動機................................................................................................................... 26
第三章 結果與討論............................................................................................................... 27
3.1 含烯丁硫官能基團之奈米粒子的合成................................................................ 27
3.1-1 聚合奈米粒子....................................................................................................... 27
3.1-2 含烯丁硫官能基團的二氧化矽粒子之製備....................................................... 30
3.1-3 烯丁硫官能基團的定量方法之設計.................................................................... 31
3.1-4 奈米粒子的合成策略之修改............................................................................... 34
3.1-5 製備具有硫醇官能基之二氧化矽粒子(8)..................................................... 37
3.1-6 製備具有丁烯硫醚官能基團之二氧化矽粒子(3)......................................... 39
3.2 釕金屬之清除測試................................................................................................ 41
3.2-1 以紫外/可見光度法對 HGII 進行偵測 ............................................................... 41
3.2-2 對市售清除劑之硫醇濃度進行定量分析........................................................... 42
3.2-3 以紫外/可見光度法來偵測金屬清除效果.......................................................... 42
3.2-4 以感應耦合電漿質譜儀來偵測金屬清除效果................................................... 44
3.3 結論........................................................................................................................ 46
第四章 引用文獻................................................................................................................... 47
第五章 實驗步驟與光譜數據............................................................................................... 50
5.1 儀器設備與藥品材料................................................................................................ 50
5.2 實驗步驟與光譜數據................................................................................................ 53
第六章光譜資料..................................................................................................................... 64
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