應用核磁共振技術觀察雙馬來亞醯胺和巴比妥酸在甲基吡咯烷酮溶劑下聚合反應的反應機制與動力學行為

NMR-Based technology to study the reaction mechanisms and Kinetic behavior of BMI and BTA polymerization in NMP

孫世勇(Shih-Yung Sun)

指導教授 ： 賈緒威

中原大學/理學院/化學研究所/碩士(2009年)

https://doi.org/10.6840/cycu200901515

摘要

核磁共振技術是一種可以分析分子級微觀化學結構的方法。在分析分子內官能基的化學位移分裂頻譜圖的資訊時，可運用特定功能的脈衝程序(例：一維圖譜，二維同核、異核圖譜)，透過化學鍵傳遞(through-bond)的J-偶合作用或空間偶極作用(through-space dipolar interaction)來推測分子內各原子核間的鍵結情形與幾何結構。
本篇主要研究的是雙馬來亞醯胺(4,4’-Bismaleimidodi-phenylmethane，以下簡稱BMI)與巴比妥酸(Barbituric Acid，以下簡稱BTA)在以甲基吡咯烷酮(N-Methyl-2-pyrrolidone，以下簡稱NMP)為溶劑時進行聚合反應的高分子化過程，並運用核磁共振脈衝程序觀察其中間物與產物，以期推測其反應機制及化學動力學行為。
操作上，首先我們運用氫、碳、Diffusion、1D-NOE、COSY、HSQC、HMBC等相關的脈衝程序來定性上將起始物BMI、BTA以及溶劑NMP做結構上的鑑定以確認樣品是否正確。由於訊號面積會正比於樣品中自旋原子核的數目，因此我們利用一維去碳偶合氫譜測量出各成分訊號的積分比例來推測BMI-BTA polymer在聚合反應時樣品量的消長，以期推測此反應在化學動力學上的行為以及可能的反應機制。定量的NMR資訊，同時提供了探討BMI-BMI、BTA-BTA、BMI-BTA polymer反應活性之比較。
最後規劃BMI與BTA在不同反應條件下(比例、時間)合成出高分子聚合物的產物，以探討不同條件對於反應在動力學上行為的多樣性。

關鍵字

核磁共振 ； 雙馬來亞醯胺 ； 巴比妥酸 ； 甲基?咯烷酮

並列摘要

Nuclear magnetic resonance (NMR) spectroscopy is one of the powerful methods that can analyze microscopic chemical structure of molecule. In order to analyze the spectral information of the chemical shift coupleing of functional group of the molecule, it is convenient to use the pulse sequences of the specific function (example: One-dimensional spectrum, two-dimentional homonuclear spectrum and two-dimentional heternuclear spectrum). To infer among each nucleus bonding situation and geometirc structure in the molecule, through J-coupling (through -bond) and the spacial dipolar interaction (through-space) that are used for information abstraction.
In this thesis, the polymerization of 4,4'-Bismaleimidodi -phenylmethane (abbreviate to BMI) and Barbituric Acid (abbreviate to BTA) were progressed in N-Methyl-2-pyrrolidone (abbreviate to NMP) solvent system. We use different specific purpose of NMR pulse sequences to observe intermediates and products, to infer mechanisms of reaction and chemical dynamics behavior where there in.
The first step is to assign the BMI and BTA structures to make sure the sample is what we expected. Here the pulse sequences we used were 1H、13C、Diffusion、1D-NOE、COSY、HSQC and HMBC. The use of 13C-decoupled 1H spectrum can induce the intergration ratio information of each compounds to infer the dynamic behavior of BMI-BTA polymerization process and to trace back the possible mechanisms of polymerization reaction. Meanwhile,the comparison of BTA-BTA、BMI-BMI、BMI-BTA interaction reactivity were also studied.
Finally, a series of studies under different reaction condition were also mentioned to show the varieties of BMI,BTA polymerization in NMP as solvent.

並列關鍵字

NMP ； BTA ； BMI ； NMR

參考文獻

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