臺灣博碩士論文加值系統

直鏈式烷基三甲基銨鹽類(Alkyltrimethyl ammonium chloride，ATMACs)為主要陽離子型界面活性劑之一，此類陽離子型界面活性劑與帶負電荷的物質表面易形成親和作用，並有殺菌效果，而適用於工業及民生用品中。但因其在缺氧環境中，物、化性及本身不易被生物分解的特質，能穩定存在於厭氧性污泥與水環境中，毒性能藉由環境中滲入到細胞粒腺體膜中，破壞生物體生物能量ATP之生產機制，促使細胞死亡，而在臺灣的年生產與使用量大約8000噸，且近年有逐年增加的趨勢，因此對於環境的污染不容小覷。此類界面活性劑主要用作潤髮乳與衣物柔軟精中，其同系物有C12-，C14-，C16-，C18-TMACs，因此針對此污染物有必要發展一套快速、穩定的分析檢測方法，來探討ATMACs在水環境中的來源與宿命。
本研究主要是以氣相層析儀之大體積進樣裝置行高溫熱裂解反應，並以離子阱質譜儀檢測欲分析之待測物，達到定性與定量之分析目的。並藉著添加過量之碘化鉀(KI)使之與水樣中之ATMACs形成離子配對，進而利用液-液相萃取方法，萃取出待測物，而在500 ml東港溪水樣中ATMACs之平均回收率分別為71％，77％，94％，72％，相對標準偏差(RSD)分別為13%、19%、16%、15%，且台灣各河水中偵測ATMACs的含量約為0.02~0.66μg/L。而日常用品中之潤髮乳與衣物柔軟精中之ATMACs以C16，C18為主，其百分比含量分別為0.19%~2.72%與0.06~5%。

This study presents a modified method to analyze alkyltrimethyl ammonium chlorides (ATMACs) in conditioners and river water. The conditioner samples were directly diluted by methanol. The procedure for water sample (adjust pH to above 10) involved mixed sample with potassium iodide (KI) as a counter-ion to enhance the extraction of ATMAC residues by dichloromethane liquid-liquid extraction. The ATMACs were then demethylation to their corresponding nonionic alkyldimethyl amines by thermal decomposition in the injection port. The corresponding alkyldimethylamines were then identified and quantitated by gas chromatograph-mass spectrometry (GC-MS) with electron impact (EI) and chemical ionization (CI) modes. The results indicate that relatively high amount of alkyldimethylamine were detected at the demethylation temperature higher than 290°C in the injection port. The method proposed herein provides a high precision and sensitivity for ATMACs, to quantitation at < 0.01 mg/L in 500 ml of the water samples. Recovery of the ATMACs in spiked various water samples ranged from 71% to 94% while RSD ranged from 7 to 21%. Concentrations of ATMACs in conditioners varied from 0.2 to 5.0%, while C16-TMAC and C18-TMAC were two major homologs. Concentrations in river waters varied from 0.02 to 0.66 mg/L. Indirect HPLC method was applied to evaluate the GC-MS method, and the compatible results were obtained.

中文摘要 ----------------------------------------------------------------------------- Ⅰ
英文摘要 ----------------------------------------------------------------------------- Ⅱ目錄 ---------------------------------------------------------------------------------- Ⅲ
表目錄 -------------------------------------------------------------------------------- Ⅵ
圖目錄 ------------------------------------------------------------------------------- Ⅶ

第一章 前言 ------------------------------------------------------------------------ 1
1-1 研究緣起 ------------------------------------------------------------------- 1
1-2 研究目標 ------------------------------------------------------------------- 4

第二章 文獻回顧 --------------------------------------------------------------- 5
2-1 陽離子型界面活性劑的分類和命名 ------------------------------- 5
2-2 陽離子型界面活性劑 --------------------------------------------------- 7
2-3 國內外相關研究 ---------------------------------------------- 7
2-4 氣相層析質譜儀 ------------------------------------------------------ 16
2-4-1氣相層析質譜儀之大體積進樣裝置系統 ----------------- 16
..2-4-2 氣相層析/離子阱質譜儀之原理與特性---------------------- 18
2-4-3 液相化學游離法(Liquid-Chemical Ionization,CI) --------- 20
2-4-3.1化學游離法之優缺點 ----------------------------------------- 22
2-5 高效能液相層析儀 ----------------------------------------------------- 23
2-6 衍生化原理 .---------------------------------------------------------------- 23
2-7水樣品萃取方法 --------------------------------------------------------- 25
第三章實驗步驟與樣品分析 ------------------------------------------------ 26
3-1 實驗藥品與儀器設備 -------------------------------------------------- 26
3-1-1 實驗藥品 --------------------------------------------------------- 26
3-1-2 儀器設備 --------------------------------------------------------- 28
3-2 實驗步驟 ------------------------------------------------------------------ 29
3-2-1 標準品的製備 -------------------------------------------------- 29
3-2-2 方法驗證萃取步驟 ---------------------------------------------- 31
3-2-3 標準品衍生化步驟 ---------------------------------------------- 31
3-2-4 真實水樣萃取及淨化 ---------------------------------------- 31
3-3氣相層析質譜儀參數設定------------------------------------------------ 32
3-4 高效能液相層析儀逆向層析管柱層析條件------------------------- 36

第四章結果與討論 -------------------------------------------------------- 37
4-1 注射埠線上(On-line)熱裂解最佳溫度探討--------------------------- 37
4-2 ATMACs之質譜測定 -------------------------------------------------- 39
4-2-1 電子撞擊法(EI)對ATMACs的探討--------------------------- 39
4-2-2 化學游離法(CI)對ATMACs的探討--------------------------- 43
4-3 ATMACs經HPLC分離的結果與討論------------------------------ 48
4-4 潤髮乳與衣物柔軟精之檢測--------------------------------------------- 49
4-4-1檢量線的製作 -------------------------------------------- 49
4-4-2 測定真實產品中之ATMACs含量--------------------- 50
4-5真實水樣品之萃取檢測---------------------------------------- 56
4-5-1 檢量線的製作-------------------------------------------------------- 56
4-5-2 ATMACs 在水環境中之萃取回收率-------------------------- 57
4-5-3 ATMACs 在不同水環境中之含量----------------------------- 68

第五章結論與建議 ------------------------------------------------------------- 62
5-1 結論 ------------------------------------------------------------------------- 62
5-2 建議 ------------------------------------------------------------------------- 62

參考文獻 ---------------------------------------------------------------------------- 63

附錄一 ------------------------------------------------------------------------------- 67
附錄二 ------------------------------------------------------------------------------- 67














表目錄
表2-1 陽離子型界面活性劑的使用範疇---------------------------------------- 8
表2-2陽離子型界面活性劑對生物體毒性濃度測試結果 -------- 9
表4-1 不同潤髮乳與衣物柔軟精中所含ATMACs之百分比含量--- 51
表4-2 不同採樣點之回收率比較------------------------------------------------ 57
表4-3 不同採樣點所含ATMACs 之濃度------------------------------------- 58












圖目錄
圖1-1 界面活性劑的種類----------------------------------------------------------- 2
圖2-1 陽離子型界面活性劑的種類 ------------------------------------------- 6
式2-1 四級銨鹽類衍生化之Hofmann Degradation------------------------- 10
式2-2 四級銨陽離子與氯離子間的親核取代反應-------------------------- 14
式2-3 四級銨鹽類熱裂解之Hofmann Degradation------------------------- 15
圖2-2 大體積進樣裝置-------------------------------------------------------------- 17
圖2-3 離子阱質譜儀裝置簡圖---------------------------------------------------- 19
圖2-4自動反應控制(ARC)操作掃瞄-------------------------------------------- 21
圖4-1 ATMACs利用電子撞擊法之最佳溫度探討-------------------------- 38
圖4-2 ATMACs利用化學游離法之最佳溫度探討-------------------------- 38
圖4-3 ATMACs經注射埠熱裂解後之選擇離子層析圖(m/z58) --------- 39
圖4-4 (A)C11-之質譜圖(B)C12-之質譜圖(C)C14-之質譜圖(D)C16-之質譜圖
(E)C18-之質譜圖------------------------------------------------------------- 42
圖4-5不同化學游離試劑與ATMACs反應之比較-------------------------- 44
圖4-6 ATMACs與CH3OH化學游離反應之質子化離子層析圖-------- 44
圖4-7 ATMACs標準品與CH3OH化學游離反應之質子化離子質譜圖..45
圖4-8 ATMACs標準品之HPLC層析圖--------------------------------------- 48
圖4-9 ATMACs標準品之檢量線------------------------------------------------- 49
圖4-10美吾髮潤髮乳之(a)EI選擇離子層析圖(b) C12，C14，C16，C18之EI質譜圖---------------------------------------------------------------------- 52
圖4-11美吾髮潤髮乳之(a)CI選擇離子層析圖(b) C12，C14，C16，C18之CI質譜圖---------------------------------------------------------------------- 53
圖4-12藥草彩虹潤髮乳之(a)EI選擇離子層析圖(m/z58)(b)C16，C18之EI質譜圖-------------------------------------------------------------------------- 54
圖4-13藥草彩虹潤髮乳之(a)CI選擇離子層析圖(m/z58)(b)C16，C18之CI質譜圖-------------------------------------------------------------------------- 55
圖4-14 ATMAC-I標準品之GC-MS檢量線---------------------------------- 56
圖4-15東港溪經萃取後，直接以GC-MS經注射埠熱裂解反應之EI(A)
選擇離子(m/z=58)層析圖(B) C12，C14，C16，C18之質譜圖----- 59
圖4-16東港溪經萃取後，直接以GC-MS經注射埠熱裂解反應之CI(A)
選擇離子(m/z=58)層析圖(B) C16，C18之質譜圖------------------- 60
圖4-17(a)空白實驗(b) ATMAC-I標準品(c)東港溪河流萃取後直接以HPLC分析-------------------------------------------------------------------- 61

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