Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3827
DC FieldValueLanguage
dc.contributor陳幹男zh_TW
dc.contributor鄭如忠zh_TW
dc.contributor.advisor戴憲弘zh_TW
dc.contributor.author黃春櫻zh_TW
dc.contributor.authorHuang, Chun-Yingen_US
dc.contributor.other中興大學zh_TW
dc.date2011zh_TW
dc.date.accessioned2014-06-06T05:32:52Z-
dc.date.available2014-06-06T05:32:52Z-
dc.identifierU0005-1908201004532200zh_TW
dc.identifier.citation1.山西省化工研究所,聚胺酯彈性體手冊,化學工業出版社,2001 2.黃微波,噴塗聚脲彈性體技術,化學工業出版社,2005 3.D. Randall and S. Lee, The Polyurethanes Book; John Wiley: New York, 2000 4. 張豐志,應用高分子手冊,五南圖書,2003 5.H. Hellbach, F. Merger and F. Towae, U.S. Pat.,4,596,679, 1984 6.G. Bohmholtd, W. Heitmann, and P. Kirechner, U.S. Pat., 5,360,931, 1993 7.R. Heitkamper, K. Konig, R. Fauss, and K. Findeisen, U.S. Pat., 4,388,238, 1983 8.M. Aresta, C. Berloco and E. Quaranta, Tetrahedron 1995, 51, 8073 9.B. Thavonekham, Synthesis 1997, 1189-1194 10.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博士論文,2008 11.W. F. Brill and N. J. Skillman, U.S. Pat. 3,763,217, 1973 12.N. Yamazaki and T. Iguchi, Polym. Sci., Polym. Chem. Ed., 1979, 17, 835-841 13.A. Michele, D. Angela and Q. Eugenio, Tetrahedron 1998, 54, 14145 14.K. Harada, R. Sugise, K. Kashiwagi and T. Matsuura, U.S. Pat., 6,143,917, 2000 15.A. Bosetti, E. Cauchi, V. Carletti and P. Cesti, U.S. Pat., 6,034,365, 2000zh_TW
dc.identifier.urihttp://hdl.handle.net/11455/3827-
dc.description.abstract此研究為改善本實驗室先前所發展以非光氣法合成聚尿素高分子之綠色製程。在新的製程中,以溶劑Tetramethylene sulfone (TMS ; bp 285℃)取代先前使用的溶劑dimethyl solfoxide (DMSO),將Diphenyl 4,4’-methylene diphenylcarbamate (DP-MDC)與長鏈聚醚二元胺(如Jeffamine)及數種不同二元胺(Diamines)直接進行聚合反應。本研究目前最合適的聚合條件為,一開始在溫度90℃下先反應1小時,此時amino group會和phenylcarbamate group進行胺化反應(Amination),之後接續使用減壓蒸餾(約7×10-3mmHg)在140℃下1-2小時移除置換出之酚以驅使反應平衡朝向胺取代進行而生成聚尿素高分子。反應結束後,將此溶液直接倒入水中即可沉澱出聚尿素高分子,溶劑TMS經蒸餾回收後,其總回收率可達90%以上。透過此製程之改進,不僅可直接製備高產率及高分子量的聚尿素高分子,並且副產物酚與溶劑TMS亦可簡便地分離與回收。zh_TW
dc.description.abstractIn this research, an improved non-phosgene process of making polyurea has been developed based on a method found previously in our laboratory. In the new process, diphenyl 4,4''-methylene diphenylcarbamate (DP-MDC), long-chained polyether diamines (eg., Jeffamines) and several different diamine extenders were carried out in the tetramethylene sulfone (TMS; bp 285 ℃) in replacing dimethyl solfoxide (DMSO) as the solvent in the polymerization. In our most desirable polymerization condition, the initial mixing temperature of 90 ℃ for 1 hours was initiated to start out the amination reaction, and that was followed by a subsequent step of vacuum distillation at about 140 ℃(under about 7×10-3mm of pressure) to drive off Phenol from the reaction mixture, in shifting the reaction equilibrium toward polyurea formation that lasted for 1-2 hours. After the distillation, the resulting polyurea was isolated by precipitation in water. TMS being a high boiling solvent could be separated from Phenol and water to recover > 90% after each runs. Through this rapid and efficient process, high yields and high molecular weights of polyurea were prepared with the recovery of the by-product and the solvent.en_US
dc.description.tableofcontents摘 要 i Abstract ii 目 錄 iii 圖 目 錄 v 表 目 錄 x 第一章 前言 1 第二章 文獻回顧 4 2-1 苯胺基甲酸苯酯(N-phenyl phenylcarbamate,PPC)的製備 4 2-2 雙苯胺基甲酸苯酯(Diphenyl 4,4''-methylene diphenylcarbamate DP-MDC)的製備 4 2-3 由雙苯胺基甲酸苯酯合成尿素的前例 5 2-4 由雙苯胺基甲酸苯酯合成聚尿素高分子 6 2-5 實驗動機 8 第三章 實驗 9 3-1 實驗藥品 9 3-2 實驗儀器 13 3-3 實驗製備步驟 15 3-3.1單體diphenyl 4,4''-methylene diphenylcarbamate (DP-MDC) 之合成實驗步驟 15 3-3.2 聚尿素高分子(PUA)之合成 16 3-3.3 使用不同鏈延長劑PUA之合成步驟 18 3-3.4 H12MDA系列PUA之合成步驟:最佳化實驗 21 3-3.5 最佳化方法應用於其他脂肪族二胺鏈延長劑之合成步驟 27 3-3.6 MDA系列PUA之合成步驟:最佳化實驗 30 3-3-7 製備聚(胺酯-尿素)高分子之合成新法 35 3-3.8 由DP-MDC合成聚(胺酯-尿素)高分子之實驗步驟 37 第四章 實驗結果與討論 39 4-1 合成單體diphenyl 4,4''-methylene diphenylcarbamate (DP-MDC) 之結果與討論 39 4-2 不同鏈延長劑PUA之結果與討論 42 4-3 H12MDA-PUA系列PUA之結果與討論 52 4-4 最佳化方法應用於其他脂肪族二胺鏈延長劑上之結果與討論 62 4-5 MDA-PUA系列PUA之結果與討論 74 4-6 由DP-MDC合成聚(胺酯-尿素)高分子之結果與討論 83 第五章 結論 92 參考文獻 94 附錄 96zh_TW
dc.language.isoen_USzh_TW
dc.publisher化學工程學系所zh_TW
dc.relation.urihttp://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-1908201004532200en_US
dc.subjectNon-phosgeneen_US
dc.subject非光氣法zh_TW
dc.subjectDiphenylcarbamatesen_US
dc.subjectPolyaminationen_US
dc.subjectPolyureaen_US
dc.subject雙苯胺基甲酸苯酯zh_TW
dc.subject聚胺化zh_TW
dc.subject聚尿素高分子zh_TW
dc.title由Diphenyl 4,4''-Methylene Diphenylcarbamate (DP-MDC) 作為前驅物應用於非光氣法製備聚尿素高分子之研究zh_TW
dc.titleA Non-phosgene Route to Polyurea Using Diphenyl 4,4''-Methylene Diphenylcarbamate (DP-MDC) as The Key Precursoren_US
dc.typeThesis and Dissertationzh_TW
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