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研究生:劉昱廷
研究生(外文):LIU, YU-TING
論文名稱:非異氰酸酯方式合成脂肪族聚氨酯之研究
論文名稱(外文):The Study of Non-Isocyanate Aliphatic Polyurethane
指導教授:芮祥鵬芮祥鵬引用關係
指導教授(外文):RWEI, SYANG-PENG
口試委員:芮祥鵬魏騰芳莊富盛
口試委員(外文):RWEI, SYANG-PENGWEI, TENG-FANGZHUANG, FU-SHENG
口試日期:2019-07-13
學位類別:碩士
校院名稱:國立臺北科技大學
系所名稱:分子科學與工程系有機高分子碩士班
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2019
畢業學年度:107
語文別:中文
論文頁數:60
中文關鍵詞:非異氰酸酯聚氨酯環碳酸酯二胺環保無毒
外文關鍵詞:Non-isocyanatePolyurethaneCyclic carbonateDiamineEnvironmental protectionNon-toxic
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非異氰酸酯聚氨酯是開闢聚合聚氨酯的另一條製程:避免使用異氰酸酯為原料,本研究先用脂肪族二胺與碳酸乙烯酯合成兩端為開環後的羥基結尾,做為硬鏈段,接著與軟鏈段PTMG1000利用酯交換縮合聚合,副產物為乙二醇;這裡使用的二胺有市售長短鏈二胺,以及本實驗室所開發的新穎二胺BAED。
本研究目的是混兩種單體為硬鏈段,與軟鏈段PTMG1000成功聚合非異氰酸酯聚氨酯,和參考文獻的性質做比較;探討實驗室開發的新穎二胺BAED(Bis(2-aminoethyl)dodecanediamide)合成NIPU的可行性,期望能取代市售昂貴的二胺。
實驗結果得知,非異氰酸酯聚氨酯有成功聚合,與用異氰酸酯合成的聚氨酯比較,製程環境穩定性佳且較環保無毒;單體選擇受熔點影響大,熔點與裂解點太近易造成聚合度不高;混兩種硬鏈段單體合成的聚氨酯,在一定比例下聚合分子量明顯提高,可以保持著斷裂應力下表現極佳的延伸率,這是比參考文獻還要來的優秀。

Non-isocyanate polyurethane is an alternative way of manufacturing polyurethane. This avoids using isocyanate as raw material, instead, we mainly use aliphatic diamine and ethylene carbonate to synthesize the hydroxyl end of the opened ring’s both ends as a hard segment, and we use a soft segment called PTMG1000 to utilize transesterification condensation polymerization. The by-product is ethylene glycol. The diamine used here is composed of commercially available long and short chain diamine and the novel diamine BAED developed by the laboratory in order to replace the currently commercially available diamine and explore feasibility of this new monomer.
The purpose of this study is to mix the hard segment composed of two monomers and the soft segment PTMG1000 to polymerize the non-isocyanate polyurethane in order to compare the properties with the references, exploring the possibility of the laboratory developed novel diamine BAED (Bis(2-aminoethyl)dodecanediamide to synthesize NIPU.
The experimental results show that the non-isocyanate polyurethane is polymerized successfully. When we compared the polyurethane synthesized with isocyanate, the stability of the working environment is higher. The condition of monomer selection is greatly affected by the fact that melting point and thermal decomposition temperature are too close to make the degree of polymerization higher. Monomer-synthesized polyurethanes also possess excellent elongation at a certain ratio.

摘要 i
Abstract ii
誌謝 iv
目錄 vii
表目錄 xi
圖目錄 xii
第一章 緒論 1
1.1 前言 1
1.2 研究目的 2
第二章 原理與文獻回顧 3
2.1 聚氨酯 3
2.1.1 聚氨酯發展歷史 3
2.1.2 聚氨酯合成原理 4
2.2 非異氰酸酯聚氨酯 5
2.2.1 非異氰酸酯聚氨酯發展歷史 5
2.2.2 非異氰酸酯聚氨酯合成原理 6
2.2.3 非異氰酸酯聚氨酯之應用 7
2.2.3.1 黏著劑 8
2.2.3.2 塗料 8
2.2.3.3 發泡塑料 9
第三章 實驗 10
3.1 實驗藥品 10
3.2 實驗設備及檢測儀器 15
3.2.1 核磁共振光譜儀
(Nuclear Magnetic Resonance Spectrometer;NMR)………………….…….16
3.2.2 傅立葉轉換紅外線光譜儀
(Fourier Transform Infrared Spectrometer;FTIR) 17
3.2.3 膠體滲透層析儀(Gel Permeation Chromatography;GPC) 18
3.2.4 X光繞射儀 (X-Ray Diffraction Analysis;XRD) 19
3.2.5 熱示差掃描卡量計 (Differential Scanning Calorimetry;DSC) 20
3.2.6 動態機械分析儀 (Dynamic Mechanical Analyzer;DMA) 21
3.2.7 熱重損失分析儀 (Thermogravimetric Analysis;TGA) 22
3.2.8 萬能拉伸試驗機 (Tensile Testing Machine) 23
3.3 實驗流程與實驗步驟 24
3.3.1 實驗流程圖 24
3.3.2 BAED之單體合成 25
3.3.3 HMDA/BAED/DADD-based diol之單體合成 26
3.3.3.1 HMDA-based diol 26
3.3.3.2 BAED-based diol 27
3.3.3.3 DADD-based diol 28
3.3.4 HBP系列之NIPU 29
3.3.4.1 HMDA-based diol + PTMG1000 29
3.3.4.2 BAED-based diol + PTMG1000 30
3.3.4.3 HMDA/BAED-based diol + PTMG1000 31
3.3.5 HDP系列之NIPU 32
3.3.5.1 DADD-based diol + PTMG1000 32
3.3.5.2 HMDA/DADD-based diol + PTMG1000 33
第四章 結果與討論 34
4.1 單體分析與鑑定 34
4.1.1 BAED 34
4.1.1.1核磁共振光譜分析 34
4.1.2 HMDA/BAED/DADD-based diol 35
4.1.2.1 核磁共振光譜分析 35
4.1.2.2 熱示差掃描分析 38
4.1.2.3 熱重損失分析 41
4.2 HBP系列之NIPU分析與鑑定 40
4.2.1 核磁共振光譜分析 40
4.2.2 傅立葉轉換紅外線光譜分析 40
4.2.3 膠體滲透層析分析 41
4.2.4 X光繞射分析 42
4.2.5 熱示差掃描分析 43
4.2.6 動態機械分析 44
4.2.7 熱重損失分析 45
4.2.8 拉伸試驗 47
4.3 HDP系列之NIPU分析與鑑定 48
4.3.1 核磁共振光譜分析 48
4.3.2 傅立葉轉換紅外線光譜分析 48
4.3.3 膠體滲透層析分析 49
4.3.4 X光繞射分析 50
4.3.5 熱示差掃描分析 51
4.3.6 動態機械分析 53
4.3.7 熱重損失分析 54
4.3.8 拉伸試驗 56
第五章 結論 57
參考文獻 58
[1]李凡, 聚酯型热塑性聚氨酯弹性体的制备及阻尼性能. 高分子材料科学与工程 2007.
[2]Six, C.; Richter, F., Isocyanates, Organic. In Ullmann's Encyclopedia of Industrial Chemistry, 2003.
[3]Daniels, R. D., Occupational asthma risk from exposures to toluene diisocyanate: A review and risk assessment. American Journal of Industrial Medicine 2018, 61 (4), 282-292.
[4]Tamami, B.; Sohn, S.; Wilkes, G. L., Incorporation of carbon dioxide into soybean oil and subsequent preparation and studies of nonisocyanate polyurethane networks. 2004, 92 (2), 883-891.
[5]Guan, J.; Song, Y.; Lin, Y.; Yin, X.; Zuo, M.; Zhao, Y.; Tao, X.; Zheng, Q., Progress in Study of Non-Isocyanate Polyurethane. Industrial & Engineering Chemistry Research 2011, 50 (11), 6517-6527.
[6]Kathalewar, M. S.; Joshi, P. B.; Sabnis, A. S.; Malshe, V. C., Non-isocyanate polyurethanes: from chemistry to applications. RSC Advances 2013, 3 (13), 4110-4129.
[7]Maisonneuve, L.; Lamarzelle, O.; Rix, E.; Grau, E.; Cramail, H., Isocyanate-Free Routes to Polyurethanes and Poly(hydroxy Urethane)s. Chemical Reviews 2015, 115 (22), 12407-12439.
[8]Cornille, A.; Auvergne, R.; Figovsky, O.; Boutevin, B.; Caillol, S., A perspective approach to sustainable routes for non-isocyanate polyurethanes. European Polymer Journal 2017, 87, 535-552.
[9]Farhadian, A.; Ahmadi, A.; Omrani, I.; Miyardan, A. B.; Varfolomeev, M. A.; Nabid, M. R., Synthesis of fully bio-based and solvent free non-isocyanate poly (ester amide/urethane) networks with improved thermal stability on the basis of vegetable oils. Polymer Degradation and Stability 2018, 155, 111-121.
[10]Painter, P.; Coleman., M., Fundamentals to Polymer Science, An Introductory Text (Second ed.). . 1998, 39.
[11]Deng, Y.; Li, S.; Zhao, J.; Zhang, Z.; Zhang, J.; Yang, W., Crystallizable and tough aliphatic thermoplastic poly(ether urethane)s synthesized through a non-isocyanate route. RSC Adv. 2014, 4 (82), 43406-43414.
[12]Li, S.; Sang, Z.; Zhao, J.; Zhang, Z.; Cheng, J.; Zhang, J., Synthesis and properties of non-isocyanate aliphatic crystallizable thermoplastic poly(ether urethane) elastomers. European Polymer Journal 2016, 84, 784-798.
[13]Bayer, O., Das Di-Isocyanat-Polyadditionsverfahren (Polyurethane). 1947, 59 (9), 257-272.
[14]Seymour, R. B.; Kauffman, G. B., Polyurethanes: A class of modern versatile materials. Journal of Chemical Education 1992, 69 (11), 909.
[15]Ashida, K., Polyurethane and related foams: chemistry and technology. CRC Press. 2006, 79–81.
[16]劉益軍, 聚氨酯樹脂及其應用. 化學工業出版社 2015.
[17]Petrović, Z. S., Polyurethanes from Vegetable Oils. Polymer Reviews 2008, 48 (1), 109-155.
[18]赵孝彬, 杜., 张小平,郑剑, 聚氨酯弹性体及其微相分离[J]. 高分子材料科学与工程 2002.
[19]Groszos, S., Method of Preparing a Polyurethane. U.S. Patent US2802022. 1957.
[20]Garipov, R.; A. Sysoev, V.; V. Mikheev, V.; I. Zagidullin, A.; Deberdeev, R.; Irzhak, V.; Berlin, A., Reactivity of Cyclocarbonate Groups in Modified Epoxy–Amine Compositions. 2003; Vol. 393, p 289-292.
[21]Figovsky, O. L., Producing Hybrid Nonisocyanate Polyurethane Networks. U.S. Patent US6120905-A. 1999.
[22]Figovsky, O. L.; Shapovalov, L. D. In Nonisocyanate polyurethanes for adhesives and coatings, First International IEEE Conference on Polymers and Adhesives in Microelectronics and Photonics. Incorporating POLY, PEP & Adhesives in Electronics. Proceedings (Cat. No.01TH8592), 21-24 Oct. 2001; 2001; pp 257-264.
[23]Rappoport, L., Use of Polymeric Precursors to Form Polyurethane based Amine for Epoxide Hardeners for Use in Coatings, Adhesives and Cements - Derived from Hydroxy Epoxide Derivatives, Diamine and Isocyanate. WIPO Patent WO9858004-A. 1999.
[24]Rappoport, L., Vainer, A.; Yam, A. New Polyfunctional Urethane- or Urea-containing Oligomer for the Preparation of Polymer Used in Adhesives, Sealants, Coatings, Composites, as well as Castable and Moldable Materials. U.S. Patent US2002169272-A1. 2001.
[25]Rappoport, L., Vainer, A.; Yam, A. Epoxy-amine Composition for Coatings, Adhesives, Comprises Epoxy Resin, Amine-curing Agents and Curing Accelerators. U.S. Patent US6465597-B1. 2003.
[26]Diakoumakos, C. D.; Kotzev, D. L., Non-Isocyanate-Based Polyurethanes Derived upon the Reaction of Amines with Cyclocarbonate Resins. 2004, 216 (1), 37-46.
[27]Mikheev, V. V.; Svetlakov, N. V.; Semenova, L. V., Water Soluble Oligo-urethane for Waterproof Coatings. USSR Patent SU1240766-A. 1987.
[28]Ohrbom, W. H. M., J. D.; Bammel, B. D.; Seaver, T. A.; Menovcik, G. G.; Harris, P. J.; Rehfuss, J. W., Curable Composition for Coatings. U.S. Patent US5766769. 1998.
[29]Birukov, O. B., D.; Figovsky, O. L.; Lekin, A.; Shapovalov, L., Liquid Oligomer Composition Containing Hydroxylamine Adducts and Method of Manufacturing Thereof. U.S. Patent US2010/0144966. 2010.
[30]王瑜; 孙元; 邓新华, 非异氰酸酯聚氨酯最新研究进展与应用. 2009, 23 (01), 11-17.
[31]Chen, C.-P.; Dai, S. A.; Chang, H.-L.; Su, W.-C.; Wu, T.-M.; Jeng, R.-J., Polyurethane elastomers through multi-hydrogen-bonded association of dendritic structures. Polymer 2005, 46 (25), 11849-11857.
[32]Javni, I.; Petrović, Z. S.; Guo, A.; Fuller, R., Thermal stability of polyurethanes based on vegetable oils. 2000, 77 (8), 1723-1734.
[33]Weng, N.-C.; Wu, C.-F.; Tsen, W.-C.; Wu, C.-L.; Suen, M.-C., Synthesis and properties of shape memory polyurethanes generated from schiff-base chain extender containing benzoyl and pyridyl rings. Des Monomers Polym 2018, 21 (1), 55-63.


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