高分子聚合物與日常生活息息相關，在合成及加工的過程中，如何有效地對其結構、化性及物性分析，對於品質管理是相當重要的一環。在分析前，通常需要較為繁瑣的前處理及層析分離方法來將目標分析物純化，以便於更進一步利用光譜分析或是質譜儀等技術進行化學組成鑑定。然而，聚合物本身的揮發性及溶解度相當低，無法直接進行游離與偵測，因此文獻中大多搭配熱裂解裝置(Pyrolyzer)的使用，先將分析物進行裂解與氣化，再導入氣相層析質譜儀(Gas chromatography/Mass spectrometry, GC/MS)進行分析；而對於高分子樣品的材料特性亦常見有使用熱重分析儀(Thermogravimetric analyzer, TGA)進行分析，透過質量與溫度之間的變化關係及逸散氣體的質譜分析可有效監測材料性能的變化。相較於傳統質譜游離法中游離源處於高度的真空環境，大氣壓力游離質譜法能夠在常溫常壓下進行游離反應，並且不受前處理及層析分離本身系統特性的限制，就能夠有效地偵測到目標分析物，不僅具有快速、即時等特點，也能夠進行高通量分析。
第一部分、熱裂解儀與大氣壓力質譜法結合介面之開發與應用
第一部分研究中致力於熱裂解法與低溫電漿游離質譜法的結合(Pyrolysis-Low temperature plasma ionization, Py-LTP)，將熱裂解後的中性分析物直接導入低溫電漿游離源，藉由氮氣所產生的活性物種，以Penning ionization的游離機制將分析物游離。研究中對於聚乙二醇(Polyethylene glycol, PEG)、雙酚A型聚碳酸酯(Polybisphenol A carbonate, PC)、纖維素，及聚乳酸(Polylactic acid)等聚合物及天然高分子進行分析，在裂解溫度400℃下都能夠得到裂解產物完整的分析物離子，而進一步將裂解溫度提高，也能夠得到其斷片及單體訊號。接著對非極性的聚乙烯(Polyethylene, PE)及正烷烴混合標準品進行分析，由文獻搜尋可知正烷烴具有相較於其他有機物較高的沸點，並且因為不具官能基，在常溫下不易游離，然而在熱裂解裝置所提供的400℃高溫下，可得到長碳鏈烷烴的[M+O-3H]+及[M-H]+氧化訊號，於600℃下更可分析碳數高達一百個以上的正烷烴，並且僅得到些微的熱裂解斷片訊號。由以上結果可得知，高溫環境可使電子及活性物種具有較高的動能，使其與分析物的碰撞機率增加，以提高低溫電漿的游離效率。
第二部分、熱重分析儀與大氣壓力質譜法結合介面之開發與應用
在傳統將熱重分析儀與質譜儀連結介面開發中，如何避免逸散氣體的冷凝及如何與質譜的高度真空環境相容為兩項重要的課題。研究中對於熱重分析法與低溫電漿游離質譜法結合介面的開發(Thermogravimetric analyzer-Low temperature plasma ionization, TGA-LTP)，為透過一自製的加熱傳輸線進行逸散氣體傳輸，其能夠將熱重分析儀中逸散的裂解產物有效地傳送至低溫電漿游離源進行游離，以乙醯水楊酸、聚己內醯胺(Polycaprolactam, PCL)，及聚丁二酸丁二醇酯的分析結果為例，在每分鐘20℃的升溫速度下從30℃升溫至650℃，可觀察到在開始重量損失及達到最大重量損失時的質譜圖變化，其中包含不同系列的裂解產物訊號；對於真實樣品的分析，以聚丙烯材質餐盤為例的結果中，除了能夠觀察到隨著程式升溫所產生的熱裂解碎片訊號，也能夠觀察到抗氧化添加劑的訊號，結果顯示此分析系統的建立能夠以線上(On-line)的方式快速檢測對於聚合物的熱穩定性及熱裂解機制。此項技術的開發將可提供高分子材料更直接且即時的分析。

Polymer is highly related to our daily life, the analysis of its structure, chemical properties, and physical poperties is very important during manufacture quality control. Analysis procedure always accompany with tedius pretreatment to purify it before further detection. However, both synthetic and natural polymer has quite low volatility and solubility, common solvent system won’t dissolve it. Therefore, many studies have focused on using pyrolysis-GC/MS for analysis by decomposing it to deectable low molecular weight compound. Thermogravimetry-MS is also one of commonly used instrument to study thermal stability of material through monitoring weight loss during heating. Compare to high vacuum operating environment in conventional mass spectrometry, atmospheric pressure ionization mass spectrometry has advantages of less or non-pretreatment, rapidness, and high throughput analysis to detect target compound with effective and less complicated methods.
At the first part of thesis, the study focused on development of interface to connect Pyrolyzer and low-temperature plasma ionization mass spectrometry, neutral pyrolysates was directly transferred to ionization source and interacted with reactive species generateed from low-temperature plasma, and proceed Penning ionization as major ionization mechanism. Poly(ethylene glycol), poly(bisphenol A carbonate), cellulose, polylactic acid and many polymer materials were analyzed under various temperature. The result show that intact oligomer molecular ions can be detected, even higher pyrosis temperature(600℃) was used, , intact pyrolysates and monomer ions still can be detected without fragment peak induced from ionization source. Non-polar polyethylene and long chain normal alkane were also analyzed, it is well known that normal alkane has higher boiling point and can’t be easily ionized under room temperature, but it can be ionized using Py-LTP MS under 400℃, spectra signal were detected as [M+O-3H]+ and [M-H]+, signal of normal alkane with carbon number up to 120 can also be detected. From above result, it can be concluded that electron and plasma species has higher kinetic energy to increase its opportunity to interact with gas phase analyte, and enhance the ionization efficiency of low-temperature plasma.
At the second part of thesis, the study focused on development of interface to connect thermogravimetry analyzer and low-temperature plasma ionization mass spectrometry, during conventional TGA-MS development, it is important to avoid condensation of evolved gas, and maintain the compatibility of high vacuum operating environment, therefore, the interface was constructed using home-made heated transfer line, and proceed ionization under ambient environment. During analysis of acetysalicyclic acid, polycaprolactam, and poly(butylene succininate), dynamic temperature was set from 30℃ to 650℃ at 20℃/min, variation of mass spectra signal can be recorded and observed with arising temperature and weight-loss. Further study on real sample, such as non-reuseable polypropyleny plate, not only Pyrolysates signal can be observed, but anti-oxidant signal from additive can also be detected. The above results show that TGA-LTP MS can rapidly monitoring thermal stability and thermal degradation mechanism on-line, provide a useful, direct, and rapid method to analyze polymer material during synthesis and development.

目錄
論文審定書 i
謝誌 ii
論文摘要 iv
Abstract vi
目錄 viii
圖次 xi
表次 xvi
符號說明表 xvii
縮寫對照表 xviii
第一章 緒論 1
一、 前言 1
1. 電噴灑游離法 (Electrospray ionization, ESI) 2
2. 大氣壓力光游離法(Atmospheric pressure photoionization, APPI) 4
3. 大氣壓力化學游離法 (Atmospheric pressure chemical ionization, APCI) 6
二、 大氣壓力微電漿游離質譜法 7
1. 尖端放電電漿(Corona discharge plasma) 10
2. 輝光放電電漿(Glow discharge plasma) 13
3. 微波誘導電漿(Microwave induced plasma, MIP) 14
4. 介電質放電電漿(Dielectric barrier discharge plasma) 15
三、 熱裂解與大氣壓力質譜法結合的發展歷史、原理及機制 19
1. 熱裂解過程與機制34 20
2. 熱裂解裝置 22
3. 熱裂解-大氣壓力質譜法之文獻回顧 26
四、 熱重分析法與大氣壓力質譜法結合的發展歷史、原理與機制 31
1. 熱重分析法 31
2. 熱重分析儀 33
3. 熱重分析-大氣壓力質譜法之文獻回顧 34
五、 研究動機與論文目標 37
第二章 熱裂解儀與低溫電漿游離質譜法結合介面之開發 38
一、 實驗 38
1. 實驗裝置 38
2. 實驗藥品 40
3. 實驗操作 41
二、 結果與討論 41
1. 低溫電漿游離源之建立 41
2. 熱裂解儀與低溫電漿游離質譜法結合介面(Py-LTP MS)之建立 42
3. 熱裂解儀與低溫電漿游離質譜法結合介面實驗參數最適化之探討 45
4. 以熱裂解儀-低溫電漿游離質譜法進行樣品分析 49
三、 結論 66
第三章 熱重分析儀與低溫電漿游離質譜法結合介面之開發 67
一、 實驗 67
1. 實驗裝置 67
2. 實驗藥品 68
3. 實驗操作 68
二、 結果與討論 69
1. 熱重分析儀與低溫電漿游離質譜法結合介面(TGA-LTP MS)之建立 69
2. 以熱重分析儀-低溫電漿游離質譜法進行樣品分析 71
三、 結論 88
參考文獻 89

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