Studies on the Reactions of Urea with Paraformaldehyde

Urea와 Paraformaldehyde 반응산물(反應産物)의 화학적(化學的) 특성(特性) 연구

The reaction of molten urea with paraformaldehyde in sealed tubes has been examined, and the concentrations of the products obtained from this reaction have been contrasted to previous results from the identical reaction carried out in open beakers. In these studies, high performance liquid chromatography(HPLC) and nuclear magnetic resonance(NMR) spectroscopy were used to analyze the products formed in the reactions. These products were biuret, triuret, dimethylenetriurea, methylenediurea, and biuretmethyleneurea. The results from the HPLC analyses showed that the concentrations of dimethylenetriurea and methylenediurea in the reaction products increased as the amount of the paraformaldehyde starting material increased. However, the amount of biuret formed in the products decreased as the paraformaldehyde concentration was increased in the urea melt. The results from the NMR analyses showed that the $NH_2$ resonance frequencies for urea, methylenediurea, and dimethylenetriurea all occurred at approximately 5.6 ppm, while the $NH_2$ frequencies for biuret and triuret occurred at approximately 6.9ppm. In the case of biuret and triuret, NH protons absorb between 8.5 and 9.5 ppm, whereas the NH protons in methylenediurea and dimethylenetriurea absorb in the 6.5-6.6ppm region. The melt reaction seems to hold promise as a different technique for ureaform preparation in general.

Urea와 Paraformaldehyde를 이용(利用)하여 Ureaform을 제조(製造)할 목적(目的)으로 이 두 성분(成分)을 혼합비율(混合比率)과 반응시간별(反應時問別)로 반응(反應)시켜 얻어진 산물(産物)의 화학적(化學的) 특성(特性)을 구명(究明)하기 위해 반응시(反應時) 생성(生成)된 물질(物質)로 예상(像想)되는 Urea, Biuret, Triuret, Methylenediurea(MDU), Dimethylenetriurea(DMTU), Biuretmethyleneurea(BMU) 등(等)에 대해 Proton-NMR Spectrometer로 분석(分析)한 결과(結果) $NH_2$기(基)의 양성자가 Urea, MDU, DMTU의 경우 5.6ppm에서, Biuret, Triuret은 6.9ppm에서 확인(確認)되었으여 또한 NH기(基)의 경우에는 Biuret, Triuret가 각각(各各) 8.5, 9.5ppm에서, MDU와 DMTU는 6.5 ~6.6ppm에서 확인(確認)되었다. 이와같이 확인(確認) 동정(同定)된 물질(物質)을 HPLC로 정량분석(定量分析)하여 반응산물간(反應産物間)에 양적(量的)인 변화(變化)를 본 시험(試驗) 결과(結果)는 MDU와 DMTU는 Paraformaldehyde의 첨가량(添加量)이 많을수록 증가(增加)하였으며 반면에 Biuret량(量)은 감소(減少)하는 경향(傾向)이었다.