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  • 學位論文

巴比妥酸與雙馬來醯胺聚合機制的探討

Investigation on the Polymerization Mechanism of N,N’-Bismaleimide-4,4’-diphenylmethane and Barbituric Acid

指導教授 : 王立義

摘要


本研究主要利用核磁共振波譜儀 (NMR) 與基質輔助雷射脫附游離飛行時間質譜儀 (MALDI-TOF) 來深入探討N,N’-(4,4’-diphenylmethane)bismaleimide (BMI)與barbituric acid (BTA)於N,N’-dimethylformamide (DMF)溶劑中,在氮氣及130°C的環境下的聚合機制。 BMI與BTA在1:1的比例下的反應產物之MALDI-TOF圖譜顯示主要質量峰之間距相同於一個BMI加上一個BTA的分子量,證實二者皆為聚合產物的單體。而產物之1H NMR、小區間的COSY以及N,N-m-phenylenedimaleimide (PMI)與BTA反應產物的DEPT135-1H NMR 2D圖譜均明確指出,BMI與BTA係以Michael addition方式進行聚合反應。另外,從PMI與BTA在1:1比例下反應產物的DEPT135-1H NMR之2D圖譜呈現了兩種二級碳訊號,但是在BMI與BTA反應的產物中,並未發現到BTA5號碳上的氫的訊號,此等顯示BTA存在了兩種反應官能基。因此我們進一步地利用5,5-dimethyl barbituric acid (5,5-DMBTA)與1,3- dimethyl barbituric acid (1,3-DMBTA)各自與BMI進行反應。產物之1H NMR圖譜顯示二者皆能與BMI進行Michael addition反應,亦即BTA中的-NH與-CH2均為reactive sites,而在PMI:BTA=1:1的產物之DEPT135與1H NMR的HSQC圖譜也發現到2.9 ppm和3.1 ppm分別是由BTA的-CH2與-NH與BMI進行反應而產生的二級碳上氫的證據,且當BTA5號碳接上第二個BMI時產生的二級碳上的氫則會出現在約3.1 ppm。而且,當我們在BMI:BTA=1:1反應過後的溶液中再加入等當量的BMI 時,整個系統在室溫下即會產生膠化現象,表示此時BTA會有第三個反應點參與反應。另外,從PMI與BTA在1:5比例下之反應產物的1H NMR圖譜,又進一步可得知BTA的第一個反應點為-CH2。 另外,我們從PMI與BTA反應的MALDI-TOF與1H NMR可直接確認BMI-BTA反應過後產生的chiral center上的氫其位置約為4.0 ppm,最後,我們利用化學軟體ChemDraw預測BMI-BTA產物尾端的BTA從原先單體的11種tautomers根據其共軛數目要最大且實際NMR的積分比例也能與預測的相符合的概念下找出最有可能出現的兩種結構。

並列摘要


The polymerization mechanism of N,N’-(4,4’-diphenylmethane)bismaleimide (BMI) and barbituric acid (BTA) in N,N’-dimethylformamide (DMF) at 130°C was investigated by using 1H NMR, COSY, HSQC and MALDI-TOF techniques. The MALDI-TOF mass spectrum of the product which was prepared from BMI and BTA at a molar ratio of 1:1 showed the mass difference of main peaks exactly equals to the sum of the molecular mass of BMI and BTA, clearly indicating both BMI and BTA are the monomers of the final polymers. Moreover, the spectra of 1H NMR, COSY of the product from BMI-BTA and the DEPT135-1H NMR 2D spectrum of the product prepared from PMI and BTA at 1:1 molar ratio reveals the polymerization was carried out via the Michael addition. Two kinds of secondary carbon signals were observed in DEPT135-1H NMR 2D spectrum of the product of PMI-BTA, implying two reactive sites may present in BTA. Therefore, 5,5-dimethyl barbituric acid (5,5-DMBTA) and 1,3- dimethyl barbituric acid (1,3-DMBTA) were employed as reactant to react with BMI. The 1H NMR spectra showed that both molecules are reactive to BMI. These findings suggest that the –NH and –CH2 moieties of BTA are reactive to the double bond of BMI. Furthermore, the 1H NMR spectrum of the product prepared from PMI and BTA at a molar ratio of 1:5 indicated that the first reactive site of BTA is –CH2.

並列關鍵字

Michael addition Barbituric acid 1HNMR MALDI-TOF

參考文獻


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