Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3761
標題: 帶有羥基及胺基甲酸苯酯之異質雙官能基的合成及其應用於非光氣法製備聚胺酯-尿素之研究
Synthesis of Hetero-difunctional Monomer Intermediate Bearing Hydroxyl and Phenyl Carbamate and It's PU Application.
作者: 張如慧
Chang, Ru-huei
關鍵字: hetero-difunctional intermediate
異質雙官能基中間體
non-phosgene
phenyl carbamate
polyurea
ployurethane-urea
非光氣法
胺基甲酸苯酯
聚尿素高分子
聚胺酯-尿素高分子
出版社: 化學工程學系所
引用: 1.D. Randall, S. Lee, The Polyurethanes Book; John Wiley: New York, 2000 2.山西省化工研究所,聚胺酯彈性體手冊,化學工業出版社,2001 3.張豐志,應用高分子手冊,五南圖書,2003 4.H. Hellbach, F. Merger, F. Towae, U.S. Patent 4,596,679, 1984 5.G. Bohmholtd, W. Heitmann, P. Kirechner, U.S. Patent 5,360,931, 1993 6.K. Ming-Chieh, T. Yen-Chen, Y. Chung-Lun, C. Hsin-Yu, J. Ru-Jong, D. Shenghong A , Macromolecules, 2008, 41, (24), 9637-9642 7.D. A. Tomalia, H. Baker, J. Dewald, M. Hall, Polymer Journal, 1985, 17 , 117 8.K. A. H. Chehade, H. P. Spielmann, Journal of Organic Chemistry, 2000, 65, 16, 4949-4953 9.D. Shenghong A, L. Hsing-Yo, W. Chien-Sheng, U.S.Patent 2008228010, 2008 10.B. M. Bhanage, S. Fujita, Y. Ikushima, M.Arai, Green Chemistry, 2003, 5, 429-432 11.Q. Li, W. Zhang, N. Zhao, W. Wei, Y. Sun, Catalysis Today, 2006, 115, 111-116 12.J. H. Clements, Industrial and Engineering Chemistry Research, 2003, 42, 663-674 13.T. Yoshino, S. Inaba, Y. Ishido, Bulledtin of the chemical society of japan, 1973, 46, 553-556 14.B. Thavonekham, Synthesis, 1997, 1189-1194 15.W. F. Brill, N. J. Skillman, U.S. Patent 3,763,217, 1973 16.N. Yamazaki, T. Iguchi, Department of Polymer Science : Polymer Chemistry Edition, 1979, 17, 835-841 17.A. Michele, D. Angela, Q. Eugenio, Tetrahedron, 1998, 14145-14156 18.K. Harada, R. Sugise, K. Kashiwagi and T. Matsuura, U.S. Patent 6,143,917, 2000 19.林照興,以綠色化學程序合成聚胺酯-脲素樹酯之中間體,國立中興大學化學工程學系,2008 20.D.A. Wicks, Z.W. Wicks, Blocked isocyanates III: Part B: Uses and applications of blocked isocyanates. Progress in Organic Coatings 2001, 41, (1-3), 1-83 21.R. Bhatt, B. Gong, F. Hong, S. Jenkins, J.P. Klein, C.T. Kohm, J.Tulinsky, U.S. Patent 7,419,984, 2008
摘要: 此研究包含了三個主題,主題一為合成帶有羥基及胺基甲酸苯酯之異質雙官能基;首先以對硝基苯酚(P-nitrophenol)為起始物,酚上的OH官能基與乙烯碳酸酯(Ethylene carbonate)進行烷烯醚化(Alkoxylation),此合成步驟產率為82%。另一苯環上的硝基官能基則在Pd/C觸媒作用下進行氫化反應獲得胺基,此步產率為93%。最後,苯環上的胺基與碳酸二苯酯(Diphenyl carbonate)進行羰基化反應(Carbonylation)可合成出產率為90%的異質雙官能基單體,Phenyl 4-(2-hydroxyethoxy)phenylcarbamate。 主題二為改善本實驗室先前所發展以非光氣法合成聚尿素樹酯之綠色化學製程,聚尿素高分子由Diphenyl 4,4’-Methylene diphenylcarbamate (簡稱DP-MDC)、聚醚二元胺(如Jeffamine)及脂肪族二元胺(Alkylene diamine)在溶劑二甲基亞碸DMSO中反應製得。此聚合反應的機制是胺基甲酸苯酯的胺化反應(Amination),反應會有副產物酚(Phenol)的生成,然而此反應所用的溶劑DMSO與副產物酚沸點相近,造成反應結束後無法將兩者分離回收。因此,改用沸點較高的溶劑環丁碸(Tetramethylene sulfone,TMS,bp:283°C/760 mmHg)取代DMSO,在聚合反應中移除酚及反應結束後TMS溶劑回收率達90%。 最後的主題三,將主題一所合成的異質雙官能基單體與本實驗室所發展的綠色製程結合加以應用於彈性體聚胺酯¬-聚尿素高分子的製備。Phenyl 4-(2-hydroxyethoxy)phenylcarbamate 先與二元異氰酸鹽預聚物先合成胺基甲酸苯酯末端官能基之預聚物。利用此預聚物與雙胺基甲酸酚酯(DP-MDC)、脂肪族二元胺進行聚胺化反應,可成功以非光氣法製備聚胺酯-尿素高分子。分子量約6萬5左右。
This study is composed of three portions. The first portion is aimed to synthesize a hetero-difunctional monomer bearing hydroxyl and phenyl carbamate. Starting from p-nitrophenol, the hydroxyl group was built by ethoxylation of the phenol OH and ethylene carbonate (yield 82%). The nitro group was subsequently hydrogenated to amino group in the presence of Pd/C catalyst (yield 93%). Finally, the target compound phenyl 4-(2-hydroxyethoxy)phenylcarbamate was obtained by carbonylation of the aryl amine with diphenyl carbonate (yield 90%). The second portion of my work was to modify the non-phosgene green process of making polyurea based on the previous method developed in our laboratory. In the old process, diphenyl 4,4'-methylene diphenylcarbamate (DP-MDC), polyether diamines (e.g., Jeffamines), and alkylene diamines were carried out in dimethyl solfoxide solution in the polyurea preparation. The polymerization occurs via amination of phenyl carbamate with elimination of phenol. Because the reaction solvent dimethyl sulfoxide has a similar boiling point to phenol, the recovery of both was not successful. In the present study, a solvent candidate, tetramethylene sulfone (TMS, bp 283°C/760 mmHg) allows the successful removal of phenol from the polyamination solution and shows a solvent recovery of more than 90%. In the last portion, the hetero-difunctional monomer was applied to the preparation of elastomeric polyurethane-urea by our newly developed green process. Phenyl 4-(2-hydroxyethoxy)phenylcarbamate was attached to an isocyanate-terminated prepolymer first. The derived polymer intermediate with phenylcarbamate terminals could be polymerized with DP-MDC, phenyl carbamate terminal prepolymer and hexamethylene diamine by the modified non-phosgene process to obtain polyurethane-urea in about with molecular weight of 65,000.
URI: http://hdl.handle.net/11455/3761
其他識別: U0005-1908200918091900
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-1908200918091900
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