臺灣博碩士論文加值系統

環氧樹脂(epoxy resin)為應用非常廣泛的熱固性樹脂，但耐衝擊性能差，無法全面滿足工程上的要求。本研究以聚脂肪二酸(dimer fatty acid)和聚醚二胺(polyetherdiamine)行聚縮合反應，製備出醚醯胺化聚脂肪二酸之增韌改質劑，然後加入環氧樹脂中，調配成90/10、80/20、70/30、60/40 (環氧樹脂/增韌改質劑 重量比)，藉由開環加成反應，使增韌改質劑以共價鍵結方式導入環氧樹脂分子結構中。實驗結果發現，硬化後環氧樹脂表面硬度、抗拉強度與抗拉模數均隨著增韌改質劑的增加而下降，抗衝擊強度與韌性則隨著增韌改質劑增加而上升，特別是在增韌改質劑添加量達到40 wt%時，增韌效果最為明顯，且未發現有相分離現象。

Epoxy resin is a widely used thermosetting resin but has poor impact resistance in some applications. In this study, carboxyl-terminated poly(ether-amide) was prepared by condensation reactions of a commercialized dicarboxylic acid and a commercialized poly(ether diamine) and was used as a toughening agent. The so-prepared toughening agent was then added into epoxy resin to have four different weight ratios of epoxy resin/toughening agent including 90/10, 80/20, 70/30, and 60/40.Upon curing at elevated temperatures, the toughening agent can be covalently incorporated into the epoxy resin via ring-opening reactions of the epoxide groups. The results found that the surface hardness, tensile strength, and Young’s modulus decreased with increasing contents of the toughening agent; the toughness and impact strength, however, increased with increasing contents of the toughening agent. In particular, the epoxy resin containing 40 wt% toughening agent exhibited the highest toughening effect without phase separations.

誌謝…………………………………………………………………..…Ⅰ
摘要………………………………………………………………….….Π
Abstract…………………………………………………………………Ⅲ
總目錄………………………………………………………………….Ⅳ
表目錄………………………………………………..…………………Ⅵ
圖目錄……………………………………………..……………………Ⅶ
Scheme目錄……………………………………………………………Ⅷ
第一章 緒論……………………………………………………………1
1.1 研究動機……………………….………………………………1
1.2 研究目的……………………….………………………………2
1.3 文獻回顧…………………….…………………………………3
第二章 理論基礎………………………………………………………6
2.1 聚脂肪二酸(dimer fatty acid)……..…………..……………….6
2.2 環氧樹脂………………...…………..…………………………9
2.2.1 環氧樹脂之定義………………………………..……………9
2.2.2 環氧樹脂的種類…………………..……..…………….…….11
2.3 環氧樹脂增韌改質劑...……………………………………..…17
2.4 環氧樹脂的增韌理論……………………………………….…21
2.5 環氧樹脂硬化反應…………………………………………….27
2.6 硬化劑的種類……………………………………………….…32
第三章 實驗部份………………………………………………...…….33
3.1 實驗設計….………………..……………………………..……33
3.1.1 增韌改質劑製備流程………………...………………….…33
3.1.2增韌環氧樹脂製備流程………………………………….…34
3.2 儀器設備……………………………...………………………35
3.3 實驗材料…………………………………………………...…37
3.4 實驗方法……………………………………...………………38
3.5 醚醯胺化二聚脂肪酸之增韌改質劑製備……………...……38
3.5.1實驗配方比例與樣品規格…………………….……………38
3.5.2 酸價測定……………………………………………………39
3.5.3 胺價測定……………………………………………………39
3.6 增軔環氧樹脂製備………………..…..…...…………………40
3.6.1 實驗配方比例與樣品規格…….…………………...………41
3.6.2 環氧當量之測定……………………...….…………………41
3.7 試片製備………………...……………………………………43
3.7.1 拉伸試片製備………………………………………………43
3.7.2 衝擊試片製備………………………….…...………………48
3.7.3 硬度試片製備………………..…..…………………………51
第四章 實驗結果與討論……………………..………………………53
4.1 結構鑑定(傅立葉紅外線光譜儀FT-IR)………..……………53
4.2 硬度試驗(Hardness)…………………………..………………59
4.3 拉伸試驗(Tensile strength)….…………………….…………..62
4.4 抗衝擊試驗(Impact strength )……………………………..….69
4.5 示差掃描熱分析儀(Differential scanning calorimeter，DSC)..73
第五章 結論…………………………..……………………….………75
第六章 參考文獻………………………………………………………76

[1] 陳逢家編著，“環氧樹脂的耐衝擊改質”，高分子工業雜誌P68-73(民國96年)。
[2] J.L Hedrick, I. Yilgor, G.L. Wilkes, J.E. McGrath, “Chemical modification of matrix Resin networks with engineering thermoplastics”, Polymer Bulletin, 13, 201-208(1985).
[3] J.L Hedrick, I. Yilgor, M.Jurek, G.L. Wilkes, J.E. McGrath, “Chemical modification of matrix resin networks with engineering thermoplastics: 1. Synthesis, morphology, physical behaviour and toughening mechanisms of poly(arylene ether sulphone) modified
epoxy networks”, Polymer, 32, 2020-2032(1991).
[4] N.Biolley, T.Pascal, B.Sillion, “Polyimide-modified epoxy system: time-temperature-transformation diagrams, mechanical and thermal properties”, Polymer, 35, 558-564(1994).
[5] D.Ratna, G.P.Simon, “Mechanical characterization and morphology of carboxyl randomized poly(2-ethyl hexyl acrylate) liquid rubber toughened epoxy resins”, polymer, 42, 7739-7747(2001).
[6] N.Chikhi, S.Fellahi, M.Baker, “Modification of epoxy resins using reactive liquid (ATBN)rubber”, European Polymer Journal, 38, 251-264(2002).
[7] W.D. Bascom, R.L. Cottington, R.L. Jones, P.J. Peyser, “The fracture of epoxy- and elastomer-modified epoxy polymers in bulk and as adhesives”,Journal Appl Polymer Sci, 19, 2545-2562(1975).
[8] Y. Huang, A.J. Kinloch,”Modelling of the toughening mechanisms in rubber-modified epoxy polymers”, Journal Mater Sci, 27, 2753-2762(1992).
[9] 陳瑋呈，”同步式與分段式互穿網型結構之環氧樹脂/交鏈CTBN奈米複材之微相形態及性質研究”，國立台灣科技大學高分子工程研究所碩士論文，P15~17(2008)。
[10] F.J. McGarry, A.M. Willner, “Toughening of an epoxy resin by an elastomeric second phase”, Ori Coat Plast Chem, 28, 512(1968).
[11] S.C. Kunz, P.W.R Beaumont,”Low-temperature behaviour of epoxy-rubber particulate composites”, Journal Mater Sci, 16, 3141-3152(1981).
[12] A.J. Kinloch, S.J. Shaw, D.A. Tod, D.L. Hunston, “Deformation and fracture behaviour of a rubber-toughened epoxy: 1. Microstructure and fracture studies”, Polymer , 24,
1341-1354(1983).
[13] A.J. Kinloch, S.J. Shaw, D.A. Tod, D.L. Hunston, “Deformation and fracture behaviour of a rubber-toughened epoxy: 2. Failure criteria”, Polymer, 24, 1355-1363(1983).
[14] K.C. Teng, F.C. Chang, “Single-phase and multiple-phase thermoplastic/thermoset polyblends: 2. Morphologies and mechanical properties of phenoxy/epoxy blends”, Polymer, 37, 2385-2394(1996).
[15] D.S. Kim, K. Cho, J.K. Kim, C.E. Kim, C.E. Park,”Effects of particle size and rubber content on fracture toughness in rubber-modified epoxies”, Polymer Eng Sci, 36, 755-768(1996).
[16] D. Ratna, AB. Samui, BC. Chakraborty, “Flexibility improvement of epoxy resin by chemical modification”, Society of Chemical Industry, 53, 1882-1887(2004).
[17] X. Zhang, W. Xu, X. Xia, Z. Zhang, R. YU,”toughening of cycloaliphatic epoxy resin by nanosize silicon dioxide”, Materials Letters, 60, 3319-3323(2006).
[18] Uniqema technology for epoxy toughening 技術資料( 2007)。
[19] X.M. Chen, B.Ellis, “Chemistry and Technology of Epoxy Resins”, Chapman & Hall, Netherlands(1993).
[20] 王德中編著，”環氧樹脂生產與應用”，化學工業出版社(民國90年)。
[21] 賴家聲編著，”高分子工業”，高立圖書有限公司(民國88年)。
[22] S. Swier, R. Pieters, B.V. Mele, “Kinetics of demixing and remixing in poly(ethylene oxide)/poly(ether sulphone) blends as studied by modulated temperature differential sanning calorimetry”, 43, 3611-3620(2002).
[23] 馬振基編著，”高分子複合材料(上)”，正中書局(1995)。
[24] 吳信玠，”熱塑性高分子微粒製備與增韌性質研究”，國立台灣大學材料科學與工程學研究所碩士論文(1999)。
[25] 垣內弘編著，”環氧樹脂應用實務”，復漢出版社(1992)。
[26] 顏昌平，”高分子粒子改質環氧樹脂韌性及破壞行為研究”，國立勤益科技大學化工與材料工程系碩士在職專班碩士論文(2010)。
[27] 詹益宏，”橡膠增韌環氧樹脂各微結構之增韌機構”，國立中央大學化學工程研究所博士論文(1990)。
[28] 廖萬達，”反應性微膠顆粒型抗收縮劑、奈米級核殼型橡膠增韌劑及蒙特納石黏土對苯乙烯/不飽和聚酯/特用添加劑三成分系之體積收縮、內部可染色性、及微觀型態結構之影響研究”，國立台灣科技大學化學工程系碩士論文(2005)。
[29] 鍾鎔聲，”高分子之IPN及semi-IPN結構之形成及物性相關性之研究”，國立台灣科技大學高分子工程研究所博士論文(2006)。
[30] A.A. Collyer, A.M. Donald, R.J. Gaymans, D. J. H ourston, H. Keskkula, S. Lane, ”Rubber toughened engineering plastics”,
pp.165-207, Chapman & Hall, UK (1994).
[31] 李柱雄，”核殼型耐衝擊改質劑合成研究”，國力交通大學應用化學系研究所博士論文(2003)。
[32] 鄭宇軒，”奈米黏土補強液態橡膠/環氧樹脂之研究”，私立逢甲大學紡織工程研究所碩士論文(2004)。
[33] J.Ma, M.S. Mo, X.S. Du, P. Rosso, K.Friedrich, H.C. Kuan, ”Effect of inorganic nanoparticles on mechanical property，fracture toughness and toughening mechanism of two epoxy systems”, Polymer , 49, 3510-3523(2008).