臺灣博碩士論文加值系統

目前應用於海運之傳統溶劑型船舶塗料不但會有溶劑汙染問題也因海洋生物及藻類附著於船體，使得船舶阻力上升並增加油耗量；因此文獻上發展出自拋光、結構釋放、酶基及表面微型工程等四類船舶塗料期望解決傳統船舶塗料所造成之問題。本研究擬結合具水解特性的丙烯酯類、矽氧烷樹脂及功能性粉末，研發具有自拋光、結構釋放和生物活性的環保水性船舶塗料。
實驗設計以反應型乳化劑和甲基丙烯酸甲酯Methyl methacrylate (MMA)、甲基丙烯酸丁酯 Butyl methacrylate (BMA)、丙烯酸-2-乙基己酯 2-Ethylhexyl Acrylate (2-EHA)以及支(R)/直鏈(S)的矽氧烷單體進行逐步添加之聚合反應，之後再加入氧化鋅、碳酸鈣、滑石粉、二氧化鈦、二氧化矽、蒙托土、氧化亞銅、DCOIT殺菌劑及分散劑等添加物，最後用鋯珠和機械攪拌分散，再噴塗塗佈厚度約為180微米塗膜進行硬度、百格試驗、水滴接觸角、粗糙度及侵蝕速率等分析。
實驗結果顯示當使用R2矽氧烷時，塗膜鉛筆硬度可以達到9H，百格試驗達0~1級，水滴接觸角達132∘以及剝落速率24.5 µm/month。

The traditional solvent-based marine coatings currently used in marine transportation not only have solvent pollution problems, but also marine organisms and algae adhere to the hull, which increases the resistance of the ship and increases fuel consumption; therefore, the literature has developed from polishing, structural release, enzyme-based and Engineered Microtopographical Surfaces types of marine coatings such as micro-engineering are expected to solve the problems caused by traditional marine coatings. This research intends to combine hydrolyzable acrylic esters, silicone resins and functional powders to develop environmentally friendly water-based marine coatings with self-polishing, structural release and biological activity..
The experimental design uses reactive emulsifiers, MMA, BMA, 2-EHA, and branched/straight-chain silicone monomers to carry out a polymerization reaction of gradual addition, and then add zinc oxide, calcium carbonate, talc, titanium dioxide, and silicon dioxide. , Montmorillonite, cuprous oxide, DCOIT antifouling agent and dispersant additives, and finally use zirconium beads and mechanical stirring and dispersion, and then spray the coating thickness of about 150 microns, the hardness, 100 grid test, Analysis of water droplet contact angle, roughness and peeling rate.
The experimental results show that when using R2 silicone, the pencil hardness of the coating film can reach 9H, the adhesion cross-cut testers can reach 0~1, the contact angle of water droplets can reach 132∘and the erosion rate of 24.5 µm/month, research shows that increased hydrophobicity can make the coating more resistant to erosion.

摘要 I
Abstract III
致謝 V
總目錄 VI
表目錄 X
圖目錄 XII
第一章緒論 1
1-1 前言 1
1-2 研究動機 2
第二章相關知識與文獻回顧 4
2-1 海洋汙垢附著的原因及過程 4
2-1-1 海洋汙垢生長的關鍵 5
2-1-2 主要的海洋汙垢生物 6
2-1-3 環境對於海洋汙垢的影響 8
2-1-4 底材對於海洋汙垢的影響 9
2-2船舶防汙漆技術 11
2-2-1 自拋光塗料(self-polishing coating, SPC) 11
2-2-2 結構釋放塗料(fouling release coating, FRC) 13
2-2-3 酶基塗料 15
2-2-4 微型表面工程塗料 16
2-3 乳液理論 20
2-3-1 聚合反應種類 21
2-3-2 乳化聚合技術 24
2-3-3 乳化聚合成核理論 30
2-3-4 一般型/反應型乳化劑 38
2-4 純丙烯酸乳液 43
2-4-1 (甲基)丙烯酸系單體 44
2-4-2水性塗料 46
2-5 最低成膜溫度 47
2-6 表面能文獻回顧 49
第三章實驗 56
3-1 實驗藥品 56
3-2 實驗設備 60
3-2-1合成裝置 60
3-2-2分析儀器 61
3-3 實驗方法 65
3-3-1 高分子合成 65
3-3-2 塗料的製備 68
3-4 測試方法 69
3-4-1 耐化學性檢測 69
3-4-2 透水性檢測 72
3-4-3 耐鹽水性試驗 75
3-4-4 鉛筆硬度 75
3-4-5 耐刷洗測試 76
3-4-6 百格試驗 79
第四章 結果與討論 81
4-1乳化聚合高分子配比及基本性質 81
4-1-1 不同軟硬單體配比對成膜的影響 81
4-1-2 乳化聚合之官能基鑑定 83
4-1-3不同矽單體/比例對粒徑大小影響 84
4-1-4清漆及不同矽單體/比例對熱穩定性的影響 86
4-1-5不同矽單體/比例對清漆硬度的影響 87
4-1-6清漆及不同矽單體/比例對之表面能的影響 87
4-1-7清漆及不同矽單體/比例對附著度的影響 89
4-2 塗料之基本性質 92
4-2-1 塗料之加熱殘份 92
4-2-2 黏度對塗料穩定性之影響 93
4-2-3 塗料之耐化學性 95
4-2-4 塗料吸水率 97
4-2-5 塗料耐鹽水性 98
4-2-6 塗料之鉛筆硬度 99
4-2-7 塗料百格試驗 100
4-2-8 塗料耐擦刷洗 102
4-2-9 塗料之表面能不同 104
4-2-10塗膜表面型態 106
4-3 N/R/S系列矽氧烷對人造海水之侵蝕速率測量 108
第五章 結論 110
5-1 結論 110
5-2 建議 113
第六章 參考文獻 114

1.Schultz, M. P.; Bendick, J. A.; Holm, E. R.; Hertel, W. M.Economic impact of biofouling on a naval surface ship. Biofouling 2011, 27, 87−98.
2.Fitridge, I.; Dempster, T.; Guenther, J.; de Nys, R. The impactand control of biofouling in marine aquaculture: a review. Biofouling 2012, 28, 649−669.
3. Yebra, D. M.; Kiil, S.; Dam-Johansen, K. Antifouling technologypast, present and future steps towards efficient and environmentally friendly antifouling coatings. Prog. Org. Coat. 2004, 50, 75−104.
4. Bressy, C.; Margaillan, A.; Faÿ, F.; Linossier, I.; Réhel, K. In advances in Marine Antifouling Coatings and Technologies; Hellio, C., Yerba, D., Eds.; Woodhead Publishing: Yebra, 2009; pp 445−491.
5.Lejars, M.; Margaillan, A.; Bressy, C. Synthesis and characterization of diblock and statistical copolymers based on hydrolyzable siloxy silylester methacrylate monomers. Polym. Chem. 2014, 5, 2109−2117.
6.Kiil, S.; Weinell, C. E.; Pedersen, M. S.; Dam-Johansen, K.Analysis of self-polishing antifouling paints using rotary experimentsand mathematical modelling. Ind. Eng. Chem. Res. 2001, 40, 3906−3920.
7.Kiil, S.; Dam-Johansen, K.; Weinell, C. E.; Pedersen, M. S.;Codolar, S. A. Dynamic simulations of a self-polishing antifouling paintexposed to seawater. J. Coat. Technol. 2002, 74, 45−54.
8.Townsin, R. L. Biofouling 2003, 19, 9.
9.Schultz, M. P.; Bendick, J. A.; Holm, E. R.; Hertel, W. M.Biofouling 2011, 27, 87.
10.Alzieu, C. L.; Sanjuan, J.; Deltreil, J. P.; Borel, M. Mar. Pollut. Bull. 1986, 17, 494.
11. Alzieu, C. Sci. Total Environ. 2000, 258, 99.
12.Terlizzi, A.; Fraschetti, S.; Gianguzza, P.; Faimali, M.; Boero, F.Aquat. Conservation: Mar. Freshwater Ecosyst. 2001, 11, 311.
13.Qian, P.-Y.; Lau, S. C. K.; Dahms, H.-U.; Dobretsov, S.; Harder,T. Mar. Biotechnol. 2007, 9, 399.
14. Haras, D. Mater. Tech. 2006, 93, s.27.
15. Li, Y.; Gao, Y. H.; Li, X. S.; Yang, J. Y.; Que, G. H. Colloids Surf.,B 2010, 75, 550.
16. Phang, I. Y.; Aldred, N.; Clare, A. S.; Vancso, G. J. J. R. Soc.Interface 2008, 5, 397.
17.Yebra, D. M.; Kiil, S.; Dam-Johansen, K. Prog. Org. Coat 2004,50, 75.
18.Hellio, C.; Yebra, D. M. Advances in Marine Antifouling Coatings and Technologies; Woodshead Publishing: Cambridge, U.K., 2009; p 1.
19.Maréchal, J.-P.; Hellio, C. Int. J. Mol. Sci. 2009, 10, 4623.
20. Cooksey, K. E.; Wigglesworth-Cooksey, B. Aquat. Microbiol. Ecol. 1995, 9, 87.
21. Dexter, S. C.; Sullivan, J. D.; Williams, J.; Watson, S. W. Appl. Microbiol. 1975, 30, 298.
22. Dexter, S. C. J. Colloid Interface Sci. 1979, 70, 346.
23. Fletcher, M.; Marshall, K. C. Adv. Microbiol. Ecol. 1982, 6, 199.
24. Fletcher, R.; Callow, M. Eur. J. Phycol. 1992, 27, 303.
25. Anderson, C. D.; Atlar, M.; Callow, M. E.; Candries, M.; Milne, A.; Townsin, R. L. J. Mar. Des. Oper. 2003, 11.
26. Omae, I. Chem. Rev. 2003, 103, 3431.
27. Bressy, C.; Margaillan, A.; Fay, F.; Linossier, I.; Rehel, K. ́ Advances in Marine Antifouling Coatings and Technologies; Woodshead Publishing: Cambridge, U.K., 2009; p 445.
28. Almeida, E.; Diamantino, T. C.; de Sousa, O. Prog. Org. Coat. 2007, 59, 2.
29. Schultz, M. P.; Kavanagh, C. J.; Swain, G. W. Biofouling 1999, 13, 323.
30. Brady, R. F. Defence Sci. J. 2005, 55, 75.
31. Noel, R. Antisoiling composition for addition to the coatings of immersed bodies and coating containing it. FR2562554, 1985.
32. Olsen, S. M.; Pedersen, L. T.; Laursen, M. H.; Kiil, S.; Dam- Johansen, K. Biofouling 2007, 23, 36933.
33. Kristensen, J. B.; Meyer, R. L.; Laursen, B. S.; Shipovskov, S.; Besenbacher, F.; Poulsen, C. H. Biotechnol. Adv. 2008, 26, 471.
34. Olsen, S. M.; Pedersen, L. T.; Hermann, M. H.; Kiil, S.; Dam-Johansen, K. Advances in Marine Antifouling Coatings and Technologies; Woodshead Publishing: Cambridge, U.K., 2009; p 623.
35. Bers, A. V.; Wahl, M. Biofouling 2004, 20, 43.
36. Schumacher, J.; Carman, M.; Estes, T.; Feinberg, A.; Wilson, L.; Callow, M.; Callow, J.; Finlay, J.; Brennan, A. Biofouling 2007, 23, 55.
37. Scardino, A.; Harvey, E.; De Nys, R. Biofouling 2006, 22, 55.
38. Scardino, A. J.; Guenther, J.; de Nys, R. Biofouling 2008, 24, 45.
39. Callow, M. E.; Jennings, A. R.; Brennan, A. B.; Seegert, C. E.; Gibson, A.; Wilson, L.; Feinberg, A.; Baney, R.; Callow, J. A. Biofouling 2002, 18, 229.
40. Eliasson, J. Lloyd’s List Event Conference: Prevention and Management of Marine Corrosion; Lloyds: London, 2003.
41. Scardino, A.; de Nys, R. Biofouling 2004, 20, 249.
42. Dafforn, K. A.; Lewis, J. A.; Johnston, E. L. Mar. Pollut. Bull. 2011, 62, 453−465.
43. R. O. Ebewele. Polymer science and technology. CRC Press,2000.
44.何衛, 金邦坤, 郭麗萍. “高分子化學實驗”. 中國：中國科學技術大學.2012. 96.
45. 孔祥正,闞成友,羅東,袁青.有機矽改性丙烯酸酯共聚乳液合成方法及膠膜性能的研究. 高等學校化學學報.1995,16(11):1810-1813.
46. C. Y. Kan, Q. Yuan, M. C. Wang, X, Z, Kong. Synthesis of Silicone-Acrylate Copolymer latexes and Their Film Properties. Polymers for Advanced Technologies.1996,7(2):95-97.
47. 楊建軍,吳慶雲,張建安, 吳明元,王輝.有機矽-丙烯酸酯共聚乳液的研究.塗料工業.2002,32(6):6-8.
48. 郭明,孫建中,周其雲.聚矽氧烷/聚丙烯酸酯共聚乳液的合成與表徵. 高校化學工程學報.2002,16(2):180-184.
49. W. D. Harkins. A General Theory of the Mechanism of Emulsion Polymerization. Journal of the American Chemical Society. 1947,69(6):1428-1444.
50. W. D. Harkins. General Theory of Mechanism of Emulsion Polymerization.II. Journal of Polymer Science.1950, 5(2): 217-251.
51. W. D. Harkins. A General Theory of the Reaction Loci in Emulsion Polymerization II. The Journal of Chemical Physics. 1946,14(1):47-48.
52. W. V. Smith, R. H. Ewart. Kinetics of Emulsion Polymerization. The Journal of Chemical Physics.1948,16(6):592-599.
53. B. Jacobi. Zur Kolloidchemie der Emulsionspolymerisation. Angewandte Chemic.1952,64(19):539-543.
54. W. J. Priest. Partice Growth in the Aqueous Polymerization of Vinyl Acetate. The Journal of Physical Chemistry.1952,56(9):1077-1082.
55. R. M. Fitch,Y. K. Kamath. Koagulationskontrolle der Teilchenzahl während der nichtwäßrigen Emulsionspolymerisation von Methylmethacrylat. Colloid and Polymer Science.1978,256(4):414.
56. J. Ugelstad, F. K. Hansen, S. Lange. Emulsion polymerization of styrene with sodium hexadecyl sulphate/hexadecanol mixtures as emulsifiers.Initiation in monomer droplets. Die Makromolekulare Chemie.1974,175(2),507-521.
57.J. Ugelstad, M. S. El-Aasser, J. W. Vanderhoff. Emulsion polymerization:Initiation of polymerization in monomer droplets. Polymer Letters Edition.1973,11(8),503-513.
58. F. K. Hansen, J. Ugelstad. Particle nucleation in emulsion polymerization.III.Nucleation in systems with anionic emulsifier investigated by seeded and unseeded polymerization. Journal of Polymer Science:Polymer Chemistry Eeition. 1979,17(10):3047-3067.
59. H. M. Ni, G. H. Ma, M. Nagai, S. Omi. Effects of ethyl acetate on the soap-free emulsion polymerization of 4-vinylpyridine and styrene I. Aspects of the mechanism. Journal of Applied Polymer Science. 2001,82(11):2679-2691.
60. H. M. Ni, http://pubs.acs.org/doi/abs/10.1021/ma010829d - ma010829dAF1Y. Z. Du, G. H. Ma, M. Nagai, S. Omi. Mechanism of Soap-Free Emulsion Polymerization of Styrene and 4-Vinylpyridine:  Characteristics of Reaction in the Monomer Phase,Aqueous Phase, and Their Interface. Macromolecules.2001,34(19):6577-6585.
61. 徐健.微乳液微觀結構和反應性表面活性劑合成及性質的研究.山東,山東大學博士論文.2001.
62. 楊性坤,栗印環.改性聚丙烯酸醋壓敏膠的研製.化學與粘合.2002,2：63-64.
63. O. Sindt, C. Gauthier, T. Hamaide, A. Guyot. Reactive surfactants in heterophase polymerization. XVI. Emulsion copolymerization of styrene–butyl acrylate–acrylic acid in the presence of simple maleate reactive surfactants. Journal of Applied Polymer Science.2000, 77(12):2768-2776.
64.殷武,孫志元,朱柯,南璇,何慶迪,張保利.丙烯酸樹脂無皂乳液的研究.塗料工業.2002,(8)：1-3.
65.張茂根,翁志學,黃志明,潘祖仁.無皂乳液的穩定性及增加穩定性的原理.高分子材料科學與工程.1999,15(5)：30-33.
66. A. Montoyagoni, D. C. Sherrington. Reactive surfactants in heterophase polymerization XXIII.Synthesis and characterizations of novel dialkyl maleate cationic surfmers. Polymer.1999,40(4)：1067-1079.
67.李維盈,淩愛蓮,桑鴻勳,呂大鵬.丙烯酸醋乳液影響因素的研究.北京工業大學學報.2002,28(2)：150-154.
68.張華騰,庾美月.塗料用純丙乳液合成的研究.上海塗料.2001, 39(4):8-10.
69.曹同玉,劉慶普,胡金生.聚合物乳液合成原理性能及應用.第二版,化學工業出版社.2007,302-304.
70. J.L. Keddie, Mater. Sci. Eng. 21 (1997) 101.
71. Y. Wang, A. Kats, D. Juhue, M.A. Winnik, R. Shivers, C. Dinsdale, Langmuir 8 (1992) 1435.
72. B.J. Roulstone, M.C. Wilkinson, J. Hearn, A. Wilson, J. Polym. Int. 21 (1991) 87.
73. Routh, A. F.; Russel, W. B. A process model for latex film formation: Limiting regimes for individual driving forces. Langmuir 1999, 15, 7762−7773.
74. Routh, A. F.; Russel, W. B. Deformation mechanisms during latex film formation: Experimental evidence. Ind. Eng. Chem. Res. 2001, 40, 4302−4308.
75. Routh, A. F.; Russel, W. B. A process model for latex film formation: Limiting regimes for individual driving forces. Langmuir 2001, 17, 7446−7447.
76. Okubo, M.; Takeya, T.; Tsutsumi, Y.; Kadooka, T.; Matsumoto, T. Asymmetric porous emulsion film. J. Polym. Sci., Polym. Chem. Ed. 1981, 19, 1−8.
77. Mallégol, J.; Bennett, G.; McDonald, P. J.; Keddie, J. L.; Dupont, O. Skin development during the film formation of waterborne acrylic pressure-sensitive adhesives containing tackifying resin. J. Adhes. 2006, 82, 217−238.
78. Chieng, B. W.; Ibrahim, N. A.; Ahmad Daud, N.; Talib, Z. A., Functionalization of Graphene Oxide via Gamma-Ray Irradiation for Hydrophobic Materials. In Synthesis, Technology and Applications of Carbon Nanomaterials, 2019; pp 177-203.
79. D.Y. Kwok1, A. W. N., Contact angle measurement and contact angle interpretation. Advances in Colloid and Interface Science 1999, 81, 167-249.
80. Young, T., III, An Essay on the Cohesion of Fluids. Philosophical Transactions of the Royal Society of London 1805, 95, 65-87.
81. Wenzel, R. N., RESISTANCE OF SOLID SURFACES TO WETTING BY WATER. Industrial & Engineering Chemistry 1936, 28 (8), 988-994.
82. Parvate, S.; Dixit, P.; Chattopadhyay, S., Superhydrophobic Surfaces: Insights from Theory and Experiment. J Phys Chem B 2020, 124 (8), 1323-1360.
83. BAXTE, A. B. D. C. A. S., WETTABILITY OF POROUS SURFACES. Transactions of the Faraday Society 1944, 40 (0), 546-551.
84. Plawsky, J. L.; Ojha, M.; Chatterjee, A.; Wayner, P. C., Review of the Effects of Surface Topography, Surface Chemistry, and Fluid Physics on Evaporation at the Contact Line. Chemical Engineering Communications 2008, 196 (5), 658-696.
85. Ennaceri, H.; Wang, L.; Erfurt, D.; Riedel, W.; Mangalgiri, G.; Khaldoun, A.; El Kenz, A.; Benyoussef, A.; Ennaoui, A., Water-resistant surfaces using zinc oxide structured nanorod arrays with switchable wetting property. Surface and Coatings Technology 2016, 299, 169-176.
86. Feng, X. J.; Jiang, L., Design and Creation of Superwetting/Antiwetting Surfaces. Advanced Materials 2006, 18 (23), 3063-3078.
87. X.-M. Li, D. Reinhoudt, M. Crego-Calama, What do we need for a superhydrophobic surface? A review on the recent progress in the preparation of superhydrophobic surfaces, Chem. Soc. Rev. 36 (2007) 1350–1368
88. U.U. Ghosh, S. Nair, A. Das, R. Mukherjee, S. DasGupta, Replicating and resolving wetting and adhesion characteristics of a rose petal, Colloids Surf. A 561 (2019) 9–17
89. B. Bhushan, M. Nosonovsky, The rose petal effect and the modes of superhydrophobicity, Philos. Trans. R. Soc. A 368 (2010) 4713–4728
90. R.D. Mukhopadhyay, B. Vedhanarayanan, A. Ajayaghosh, Creation of “rose petal” and “lotus leaf” effects on alumina by surface functionalization and metal-ion coordination, Angew. Chem. Int. Ed. 56 (2017) 16018–16022
91.Y. Li, R. Chen, Y. Feng, L. Liu, X. Sun, L. Tang, K. Takahashi, J. Wang. Antifouling behavior of self-renewal acrylate boron polymers with pyridine-diphenylborane side chains New J. Chem., 42 (2018), pp. 19908-19916
92. S. Chen, C. Ma, G. Zhang Biodegradable polymer as controlled release system of organic antifoulant to prevent marine biofouling Prog. Org. Coat., 104 (2017), pp. 58-63
93. S.H. Kwon, I. Lee, H. Park, S.G. Lee Decomposition mechanisms of self-polishing copolymers for antifouling coating materials through first-principles approach Prog. Org. Coat. (2019), p. 105406
94. M. Lejars, A. Margaillan, C. Bressy Fouling release coatings: a nontoxic alternative to biocidal antifouling coatings Chem. Rev., 112 (2012), pp. 4347-4390
95.Ou, M. Chen, Y. Guo, Y. Kang, Y. Guo, S. Zhang, J. Yan, Q. Liu, D. Li. Preparation of novel marine antifouling polyurethane coating materials. Polym. Bull., 75 (2018), pp. 5143-5162
96.C. Howell, T.L. Vu, J.J. Lin, S. Kolle, N. Juthani, E. Watson, J.C. Weaver, J. Alvarenga, J. Aizenberg. Self-replenishing vascularized fouling-release surfaces. ACS Appl. Mater. Interfaces, 6 (2014), pp. 13299-13307.
97. .F. Estarlich, S.A. Lewey, T.G. Nevell, A.A. Thorpe, J. Tsibouklis, A.C. Upton. The surface properties of some silicone and fluorosilicone coating materials immersed in seawater Biofouling, 16 (2000), pp. 263-275.
98. X. Yang, C. Ding, M. Wu, X. Xu, X. Ke, H. Xu. Biomineral interface with superior cell adhesive and antibacterial properties based on enzyme-triggered digestion of saliva acquired, Chem. Eng. J. 15, (2021), 128955.
99. M.R. Esfahani, E.M. Languri, M.R. Nunna Effect of particle size and viscosity on thermal conductivity enhancement of graphene oxide nanofluidInt. Commun. Heat Mass Transfer, 76 (2016), pp. 308-315
100. X. Hu, Y. Yu, W. Hou, J. Zhou, L. Song Effects of particle size and pH value on the hydrophilicity of graphene oxide Appl. Surf. Sci., 273 (2013), pp. 118-121
101. F. Zhan, M. Youssef, J. Li, B. Li. Beyond particle stabilization of emulsions and foams: Proteins in liquid-liquida and liquid-gas interfaces Appl. Surf. Sci., 273 (2022), 102743
102. I. Yamamoto, Fluorinated Polymers, Chapter 2: Fluoroalkyl Acrylate Polymers and Their Applications, Fluorinated Polymers, Polymer Chemistry Series 2 (2017) 32-53.
103. P.K. Dhal, G.N. Babu, J.C.W. Chien Resist polymers: part VII thermolysis of fluoroalkyl methacrylates Polym. Degrad. Stabil., 16 (1986), pp. 135-145
104. V. Castelvetro, M. Raihane, S. Bianchi, S. Atlas, I. Bonaduce Thermal degradation behaviour of a nearly alternating copolymer of vinylidene cyanide with 2,2,2-trifluoroethyl methacrylate Polym. Degrad. Stab., 96 (2011), pp. 204-211