本研究使用預聚物混合法及倒相分散法成功製備了一系列低黏度、高穩定性的水性聚氨酯分散液。首先使用多元醇聚四氫呋喃(polytetramethylene ether glycol, PTMG)、親水離子基團2,2-二羥甲基丙酸(dimethylolpropionic acid, DMPA)和過量的二異氰酸酯氫化苯基甲烷二異氰酸酯(hydrogenated diphenylemthane diisocyanate, H12MDI)合成出預聚物後，利用三乙胺(triethylamine, TEA)中和，隨後加入去離子水進行水分散，最後以不同莫耳比的鏈延長劑乙二胺(ethylenediamine, EDA)和間苯二甲胺(m-Xylylenediamine, MXDA)進行鏈延長，獲得固含量大約為40%之水性聚胺酯分散液，並探討不同NCO/OH莫爾比、親水基團用量和鏈延長劑比例。利用傅立葉傳換紅外線光譜儀 (FT-IR)鑑定所合成水性聚氨酯之化學結構，證實聚合反應已成功進行，藉由奈米粒徑分析儀、pH計、黏度計、萬能拉伸試驗機、微差掃描熱計(DSC)、熱重分析儀(TGA)及吸水率測試等，以探討水性聚氨酯之性能。研究結果顯示，當R值為2.0、親水離子基團含量為4%時，其粒徑及黏度分別為100.2 nm和32.2 cP，並擁有較佳的儲存穩定性及低黏度。藉由熱分析顯示出水性聚氨酯的熱性能隨著MXDA的添加，其玻璃轉換溫度和熱降解溫度都有所提升。

In this work, a series of low viscosity and high stability waterborne polyurethanes (WPU) were successfully prepared by prepolymer process and phase inversion method. The NCO-terminated prepolymer was synthesized by using polytetramethylene ether glycol (PTMG), hydrophilic di-ol monomer dimethylolpropionic acid (DMPA) and an excess of 4,4-diisocyanatodicyclohexylmethan (H12MDI). After neutralized by TEA, then dispersed in deionized water, finally extended chain agents ethylenediamine (EDA) and m-Xylylenediamine (MXDA) with different molar ratios. WPU dispersion with solid content of 40 wt% was obtained. To explore the effect of the NCO/OH molar ratio, hydrophilic group content and chain extender agents molar ratio on the viscosity of WPU was investigated. The chemical structures of the waterborne polyurethane were characterized by infrared spectroscopy (FT-IR), which confirmed that the polymerization reaction had been successfully carried out. To discuss the performance of water-based polyurethane by nanometer particle size analyzer, pH meter, viscosity meter, universal tensile testing machine ,differential scanning calorimeter (DSC), thermogravimetric analyzer (TGA) and water absorption test. The research results show that when the R value is 2.0 and the hydrophilic ionic group content is 4 wt %, the particle size and viscosity are 100.2 nm and 32.2 cP, respectively, and it has better storage stability and low viscosity. And thermal analysis also shows that the thermal properties of waterborne polyurethane with the addition of MXDA, its glass transition temperature and thermal degradation temperature have improved.

摘要 I
Abstract III
致謝 V
總目錄 VI
流程目錄(Scheme) X
表目錄(Table) XI
圖目錄(Figure) XIII
第一章 緒論 1
1-1 前言 1
1-2 研究動機 2
第二章 文獻回顧 3
2-1 水性聚氨酯 (Waterborne Polyurethane, WPU) 3
2-1-1 聚氨基甲酸酯 3
2-1-2 聚胺基甲酸酯乳化技術 5
2-1-3 聚氨基甲酸酯的合成方法 5
2-1-4 水性聚胺酯種類 14
2-2水性聚氨酯的基本組成 15
2-2-1 異氰酸酯 (isocyanate) 15
2-2-2 多元醇 (polyol) 20
2-2-3 親水離子基團 (hydrophilic ionic group) 22
2-2-4 鏈延長劑 (chain extander) 23
2-2-5 中和劑 (neutralizer) 24
2-2-6 觸媒 (catalysts) 24
2-3 影響水性聚氨酯性質之因素 26
2-3-1 異氰酸酯種類之影響 26
2-3-2 多元醇種類之影響 26
2-3-3 親水離子基團種類及含量之影響 28
2-3-4 不同R值(NCO/OH 莫耳比)之影響 29
2-3-5 催化劑種類之影響 29
2-3-6 中和劑種類之影響 30
2-3-7 鏈延長劑種類之影響 30
2-3-8 水性聚氨酯之合成 31
第三章 實驗 32
3-1 實驗流程圖 32
3-2 材料與藥品 33
3-2-1 藥品 33
3-2-2 滴定藥品 34
3-3 實驗裝置 35
3-4 儀器設備 36
3-5 實驗步驟 39
3-5-1 合成步驟 39
3-5-2 NCO官能基濃度測定 41
3-5-3樣品命名 42
3-5-4 水性聚氨酯薄膜製備 42
第四章 結果與討論 43
4-1 水性聚胺酯之結構鑑定 43
4-1-1 水性聚氨酯之結構鑑定 43
4-1-2 水性聚氨酯之酸鹼值 45
4-2 水性聚氨酯不同R值(NCO/OH molar ratio)之物性探討 46
4-2-1 不同R值(NCO/OH molar ratio)對粒徑和粒徑分布之影響 46
4-2-2 不同R值(NCO/OH molar ratio)對粒徑和黏度之影響 48
4-2-3 不同R值(NCO/OH molar ratio)對吸水率、水溶解率和大顆粒體積百分比之影響 49
4-3 水性聚氨酯不同親水離子基團含量(DMPA %)之物性探討 51
4-3-1 不同親水離子基團含量(DMPA%)對粒徑和粒徑分布之影響 51
4-3-2 不同親水離子基團含量(DMPA%)對粒徑和黏度之影響 52
4-3-3 不同親水離子基團含量(DMPA%)對水溶解率、吸水率和大顆粒體積百分比之影響 54
4-4 水性聚氨酯不同MXDA含量(MXDA mole/MXDA+EDA mole)之物性及熱性能探討 55
4-4-1 不同MXDA含量(MXDA mole/MXDA+EDA mole)對粒徑和粒徑分布之影響 55
4-4-2 不同MXDA含量(MXDA mole/MXDA+EDAmole)對粒徑和黏度之影響 57
4-4-3 不同MXDA含量(MXDA mole/MXDA+EDA mole)對吸水率、水溶解率和大顆粒體積百分比之影響 58
4-4-4 不同MXDA含量(MXDA mole/MXDA+EDA mole)對拉伸測試之影響 60
4-4-5 不同MXDA含量(MXDA mole/MXDA+EDA mole)對熱性能之影響 61
4-4-6 不同MXDA含量(MXDA mole/MXDA+EDA mole)對熱穩定性之影響 63
第五章 結論 68
第六章 參考文獻 69

1. M.B.C. Fernanda, C.D. Marcia and S.A. Lairton, Anionic waterborne polyurethane dispersions based on hydroxyl-terminated polybutadiene and poly(propylene glycol): Synthesis and characterization, Journal of Applied Polymer Science, 80(4), 566-572, 2001.
2. Y.H. Young, E.J. Kim and H.D. Kim, Synthesis and properties of waterborne poly(urethane urea)s containing polydimethylsiloxane, Journal of Applied Polymer Science, 120(1), 212-219, 2011.
3. S. Zhang, H. Lv, H. Zhang, B. Wang and Y. Xu, Waterborne polyurethanes: Spectroscopy and stability of emulsions, Journal of Applied Polymer Science, 101(1), 597-602, 2006.
4. X. Zhou, Y. Li, C. Fang, S. Li, Y. Cheng, W. Lei and X. Meng, Recent Advances in Synthesis of Waterborne Polyurethane and Their Application in Water-based Ink: A Review, Journal of Materials Science & Technology, 31(7), 708-722, 2015.
5. M.M. Rahman, H.H. Chun and H. Park, Waterborne polysiloxane–urethane–urea for potential marine coatings, Journal of Coatings Technology and Research, 8(3), 389-399, 2011.
6. B. Vogt-Birnbrich, Novel synthesis of low VOC polymeric dispersions and their application in waterborne coatings, Progress in Organic Coatings, 29(1), 31-38, 1996.
7. M.M. Rahman and H.D. Kim, Synthesis and characterization of waterborne polyurethane adhesives containing different amount of ionic groups (I), Journal of Applied Polymer Science, 102(6), 5684-5691, 2006.
8. J.O. Akindoyo, M.D. Beg, S. Ghazali, M.R. Islam, N. Jeyaratnam and A.R. Yuvaraj, Polyurethane types, synthesis and applications – a review, RSC Advances, 6(115), 114453-114482, 2016.
9. J. Vadillo, I. Larraza, A. Arbelaiz, M.A. Corcuera, M. Save, C. Derail and A. Eceiza, Influence of the addition of PEG into PCL-based waterborne polyurethane-urea dispersions and films properties, Journal of Applied Polymer Science, 137(26), 48847, 2020.
10. F.M.B. Coutinho, M.C. Delpech, T.L. Alves and A.A. Ferreira, Degradation profile of films cast from aqueous polyurethane dispersions, Polymer Degradation and Stability, 70(1), 49-57, 2000.
11. D.J. Hourstion, G. Williams, R. Satguru, J.D. Padget and D. Pears, Structure–property study of polyurethane anionomers based on various polyols and diisocyanates, Journal of Applied Polymer Science, 66, 2035-2044, 1997.
12. C.H. Shao, J.J. Huang, G.N. Chen J.T. Yeh and K.N. Chen, Thermal and combustion behaviors of aqueous-based polyurethane system with phosphorus and nitrogen containing curing agent, Polymer Degradation and Stability, 65(3), 359-371, 1999.
13. J.W. Rosthauser and K. Nachtkamp, Waterborne Polyurethanes, Journal of Coated Fabrics, 16(1), 39-79, 1986.
14. D. Dieterich, Aqueous emulsions, dispersions and solutions of polyurethanes; synthesis and properties, Progress in Organic Coatings, 9(3), 281-340, 1981.
15. S. Ramesh, K. Tharanikkarasu, G.N. Mahesh and G. Radhakrishnan, Synthesis, physicochemical characterization, and applications of polyurethane ionomers: A review,Journal of Macromolecular Science, 38, 481-509, 1998.
16. G.L. Flickinger, I.S. Dairanieh and C.F. Zukoski, The rheology of aqueous polyurethane dispersions, Journal of non-newtonian fluid mechanics, 87(2-3), 283-305, 1999.
17. D. Dieterich and K. Uhlig, Polyurethanes, Ullmann’s encyclopedia of industrial chemistry, Elvers, B, 665, 1992.
18. B.K. Kim and J.C. Lee, Waterborne polyurethanes and their properties, Journal of Polymer Science Part A: Polymer Chemistry, 34(6), 1095-1104, 1996.
19. B.S. Kim and B.K. Kim, Enhancement of hydrolytic stability and adhesion of waterborne polyurethanes, Journal of Applied Polymer Science, 97(5), 1961-1969, 2005.
20. H. Honarkar, Waterborne polyurethanes: A review, Journal of Dispersion Science and Technology, 39(4), 507-516, 2018.
21. V. Mishra, I. Mohanty, M.R. Patel and K.I. Patel, Development of Green Waterborne UV-Curable Castor Oil-Based Urethane Acrylate Coatings: Preparation and Property Analysis, International Journal of Polymer Analysis and Characterization, 20(6), 504-513, 2015.
22. B.K. Kim and Y.M. Lee, Aqueous dispersion of polyurethanes containing ionic and nonionic hydrophilic segments, Journal of applied polymer science, 54(12), 1809-1815, 1994.
23. M.M. Rahman and W.K. Lee, Properties of isocyanate-reactive waterborne polyurethane adhesives: Effect of cure reaction with various polyol and chain extender content, Journal of Applied Polymer Science, 114(6), 3767-3773, 2009.
24. C. Prisacariu, Polyurethane elastomers: from morphology to mechanical aspects. Springer Science & Business Media, 2011.
25. E. Sharmin and F. Zafar, Polyurethane: an introduction, Polyurethane, 3-16, 2012.
26. S.A.Madbouly and J.U. Otaigbe, Recent advances in synthesis, characterization and rheological properties of polyurethanes and POSS/polyurethane nanocomposites dispersions and films, Progress in Polymer Science, 34(12), 1283-1332, 2009.
27. M.S. Yen and P.Y. Tsai, Effects on the structure and properties of membranes formed by blending polydimethylsiloxane polyurethane into different soft-segment waterborne polyurethanes, Journal of Applied Polymer Science, 102(1), 210-221, 2006.
28. J.H. Jeong, Y.C. Han, J.H. Yang, D.S. Kwak and H.M. Jeong, Waterborne polyurethane modified with poly(ethylene glycol) macromer for waterproof breathable coating, Progress in Organic Coatings, 103, 69-75, 2017.
29. S.L. Huang and J.Y. Lai, Structure-tensile properties of polyurethanes, European Polymer Journal, 33(10), 1563-1567, 1997.
30. A. Saralegi, A. Etxeberria, B.F. Arlas, I. Mondragon, A. Eceiza and M.A. Corcuera, Effect of H12MDI isomer composition on mechanical and physico-chemical properties of polyurethanes based on amorphous and semicrystalline soft segments, Polymer Bulletin, 70(8), 2193-2210, 2013.
31. R.S. Dearth , H. Mertes, and P.J. Jacobs, An overview of the structure/property relationship of coatings based on 4,4′-dicyclohexyl-methane diisocyanate (H12MDI), Progress in Organic Coatings, 29(1), 73-79, 1996.
32. R. Li and Z. Shan, Research on structural features and thermal conductivity of waterborne polyurethane, Progress in Organic Coatings, 104, 271-279, 2017.
33. B. Löwenhaupt and G.P. Hellmann, Microphase and macrophase separation in blends with a two-block copolymer, Polymer, 32(6), 1065-1076, 1991.
34. S. Li, Z. Liu, L. Hou, Y. Chen and T. Xu, Effect of polyether/polyester polyol ratio on properties of waterborne two-component polyurethane coatings, Progress in Organic Coatings, 141, 105545, 2020.
35. H. Wang, Y. Zhou, M. He and Z. Dai, Effects of soft segments on the waterproof of anionic waterborne polyurethane, Colloid and Polymer Science, 293(3), 875-881, 2014.
36. J. Zhu, Z. Wu, D. Xiong, L. Pan and Y. Liu, Preparation and properties of a novel low crystallinity cross-linked network waterborne polyurethane for water-based ink, Progress in Organic Coatings, 133, 161-168, 2019.
37. J.T. Garrett, R. Xum J. Cho and J. Runt, Phase separation of diamine chain-extended poly(urethane) copolymers: FTIR spectroscopy and phase transitions, Polymer, 44(9), 2711-2719, 2003.
38. W.K. Liu, Y. Zhao, R. Wang, F. Luo, J.S. Li, J.H. Li and H. Tan, Effect of Chain Extender on Hydrogen Bond and Microphase Structure of Biodegradable Thermoplastic Polyurethanes, Chinese Journal of Polymer Science, 36(4), 514-520, 2018.
39. Y.H. Guo, J.J. Guo, H. Miao, L.J. Teng and Z. Huang, Properties and paper sizing application of waterborne polyurethane emulsions synthesized with isophorone diisocyanate, Progress in Organic Coatings, 77(5), 988-996, 2014.
40. Y.H. Guo, S.C. Li, G.S. Wang, W. Ma and Z. Huang, Waterborne polyurethane/poly(n-butyl acrylate-styrene) hybrid emulsions: Particle formation, film properties, and application, Progress in Organic Coatings, 74(1), 248-256, 2012.
41. R.H. Patel and P.M. Kapatel, Studies on Influence of the Size of Waterborne Polyurethane Nanoparticles on Coating Performance, Materials Today: Proceedings, 18, 1548-1555, 2019.
42. W.T. Lin and W.J. Lee, Effects of the NCO/OH molar ratio and the silica contained on the properties of waterborne polyurethane resins, Colloids and Surfaces A: Physicochemical and Engineering Aspects, 522, 453-460, 2017.
43. S.M. Cakić, G.S. Nikolić and J.V. Stamenković, The Thermal Degradation of Waterborne Polyurethanes with Catalysts of Different Selectivity, Polymer-Plastics Technology and Engineering, 46, 299-304, 2007.
44. Y.S. Kwak, S.W. Park and H.D. Kim, Preparation and properties of waterborne polyurethane?urea anionomers?influences of the type of neutralizing agent and chain extender, Colloid & Polymer Science, 281(10), 957-963, 2003.
45. Y. Chen and Y.L. Chen, Aqueous dispersions of polyurethane anionomers: Effects of countercation, Journal of Applied Polymer Science, 46(3), 435-443, 1992.
46. M.C. Delpech and F.M.B. Coutinho, Waterborne anionic polyurethanes and poly(urethane-urea)s: influence of the chain extender on mechanical and adhesive properties, Polymer Testing, 19(8), 939-952, 2000.
47. L. Lei, L. Zhong, X. Lin, T. Li and Z. Xia, Synthesis and characterization of waterborne polyurethane dispersions with different chain extenders for potential application in waterborne ink, Chemical Engineering Journal, 253, 518-525, 2014.
48. F.M.B. Coutinho, M.C. Delpech, T.L. Alves and A.A. Ferrera, Degradation profiles of cast films of polyurethane and poly(urethane-urea) aqueous dispersions based on hydroxy-terminated polybutadiene and different diisocyanates, Polymer Degradation and Stability, 81(1), 19-27, 2003.
49. B.K. Kim, T.K. Kim and H.M. Jeong, Aqueous dispersion of polyurethane anionomers from H12MDI/IPDI, PCL, BD, and DMPA, Journal of Applied Polymer Science, 53(3), 371-378, 1994.
50. J.H. Huh, H.I Kim, M.M. Rahman and H.D. Kim, Preparation and properties of MDI/H12MDI-based water-borne poly(urethane-urea)s—Effects of MDI content and radiant exposure, Journal of Applied Polymer Science, 110(6), 3655-3663, 2008.
51. C.P. Chai, Y.F. Ma, G.P. Li, Z. Ge, S.Y. Ma and Y.J. Luo, The preparation of high solid content waterborne polyurethane by special physical blending, Progress in Organic Coatings, 115, 79-85, 2018.
52. S.K. Lee and B.K. Kim, High solid and high stability waterborne polyurethanes via ionic groups in soft segments and chain termini, Journal of Colloid and Interface Science, 336(1), 208-214, 2009.
53. Q.A. Li and D.C. Sun, Synthesis and characterization of high solid content aqueous polyurethane dispersion, Journal of Applied Polymer Science, 105(5), 2516-2524, 2007.
54. Z Zhu, R. Li, C. Zhang and S. Gong, Preparation and Properties of High Solid Content and Low Viscosity Waterborne Polyurethane-Acrylate Emulsion with a Reactive Emulsifier, Polymers (Basel), 10(2), 2018.
55. M.M. Rahman, H.D. Kim, and W.K. Lee, Properties of Waterborne Polyurethane Adhesives: Effect of Chain Extender and Polyol Content, Journal of Adhesion Science and Technology, 23(1), 177-193, 2009.
56. S.J. Peng, Y. Jin, X.F. Cheng, T.B. Sun, R. Qi and B.Z. Fan, A new method to synthesize high solid content waterborne polyurethanes by strict control of bimodal particle size distribution, Progress in Organic Coatings, 86, 1-10, 2015.
57. ASTM D2572-97
58. 廖政佳，不同硬鏈段含量對水性聚氨基甲酸酯之熱裂解探討，私立逢甲大學紡織工程研究所，2005。
59. C. 赫普伯恩，聚氨酯彈性體，烃加工出版社，1987。
60. 山西省化工研究所，聚氨酯彈性體手冊，化學工業出版社，2012。
61. 李崇維，無溶劑、低黏度、高固形份水性聚氨酯之製備及其物性之研究，國立高雄科技大學化學工程與材料工程系，碩士論文，2019。
62. 邱詠翔，對苯二甲胺擴鏈劑對水性PU性質之影響，國立高雄應用科技大學化學工程與材料工程系，碩士論文，2018。