應用核磁共振技術探討馬來亞醯胺及巴比妥酸在二甲基甲醯胺溶劑下聚合反應過程的反應機制

Study of the Polymerization Mechanisms of BMI and BTA in DMF via NMR-based technology

蘇原群(Yuan-Chun Su)

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/cycu200901516

摘要

核磁共振技術可測量多種不同的自旋原子核，而其中自旋原子核的訊號位置及分裂圖形與其周圍化學環境是息息相關的。藉由核磁共振技術測得不同的化學位移位置可獲得化學鍵結的訊息。而综合核磁共振圖譜的化學位移(chemical shift)、J偶合(J-coupling)、積分值(quantitative integration)、擴散係數值(Diffusion coefficient)、二維相關頻譜技術(2D corrected spectroscpoy)實驗結果可推論出樣品的分子結構。
液態核磁共振技術具：(一)多樣性的脈衝程序(一維與多維同核或異核pluse sequences)、(二)高解析度(NMR可分辨1Hz 的差異。與IR相比，1 cm1＝3×1010 Hz)、(三)可分辨混合物(利用COSY脈衝程序或不同的Diffusion coefficient值)、(四)可同時定性及定量決定分子特性的特點。因此核磁共振技術是分子結構鑑定的一大利器。除了熱力學上確定分子結構的功能之外，核磁共振技術亦可討論動力學部份，藉由反應物活性基及生成物的結構鑑定可推論聚合反應時的反應機制。
傳統上高分子合成注重其功能及表現，而對於其微結構並無深入探討。本篇研究雙馬來亞醯胺(4,4’-Bismaleimidodi-phenylmethane)和巴比妥酸(Barbituric acid)在二甲基甲醯胺(N,N-Dimethylformamide)溶劑中，進行聚合反應(Polymerization)過程的可能反應機制。在之前文獻中提到雙馬來亞醯胺可能進行之反應機制有單體聚合反應(homopolymerization reaction)、麥可加成反應(Michael addition reaction)、開環反應(ring-opening aminolysis reaction)、酮基自由基反應(ketone radical reaction)；本篇利用核磁共振技術佐以其他配合之測量技術對BMI-BTA聚合物進行分子結構鑑定，進而推導可能的反應機制，並希望依此改進製程，以期未來針對BMI-BTA聚合反應做改質、微觀調控，並應用在不同領域。

關鍵字

核磁共振 ； 二甲基甲醯胺 ； 馬來亞醯胺 ； 巴比妥酸

並列摘要

Nuclear magnetic resonance technology can measure a variety of spin nuclei, meanwhile the information is closely related to its chemical environments. It is therefore if we can know its information of linking chemical bond of nuclei with the chemical shifts ,(we might confirm the thermodynamic molecular structure of the sample) by the combination chemical shift、 J-coupling、 quantitative integration、 diffusion coefficient.
Liquid nuclear magnetic resonance has the following characteristics like (1) high resolution (1Hz resolution in NMR equals to 3.3*1011cm1 resolution in IR ) ,(2) mixture compounds analysis(by using COSY or diffusion coefficient measurement expts) ,(3) simultaneously qualitative and quantitative analysis available,(4) diversified pulse sequence to extract different types of through-bond and through-space information (could be one-dimension, 2D homonuclear and 2D heteronuclear pluse sequences),(5) thermodynamic structural identification and dynamic behavior study.it is therefore that NMR is important to the structural identification at a molecular level. In addition the molecular structural identification, NMR can also perform dynamic study, to infer the possible reaction mechanisms by a comprehensive understand of the reactant active sites and the structures of products.
Traditionally, polymer chemists focus on the behaviors and utility functions of the polymers, which does not have deep discussion to its molecular structure. In this thesis, we studied the possible reaction mechanisms through the polymerization process of which BMI (4,4'-Bismaleimidodi-phenylmethane) interacts with BTA (Barbituric acid) in DMF (N,N-Dimethylformamide) solvent system. Some previous studies showed that BMI could undergo the processes of homopolymerization reaction, Michael addition reaction, ring-opening aminolysis reaction and ketone radical reaction. In this paper we identified the structures of BMI-BTA polymer and the possible reaction mechanism by mainly NMR technology and some complementary measurements. It is our wish to improve reaction efficiency, to fine tune the modification of BMI-BTA polymer in the future and hopefully applied this technique to different domains.

並列關鍵字

DMF ； NMR ； BMI ； BTA

參考文獻

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