臺灣博碩士論文加值系統

本文目的主要為探討三種特用添加劑，分別為：(1)奈米級及次微米級核殼型橡膠(core-shell rubber) (2)無機矽膠/有機高分子核殼型顆粒及(3)有機化改質蒙特納石黏土(Montmorillonite clay，MMT)，其對苯乙烯/不飽和聚酯(或乙烯基酯)/特用添加劑三成份系統及環氧樹脂/硬化劑/特用添加劑三成份系統之反應前相容性，聚合固化反應動力，玻璃轉移溫度、微觀型態結構、抗體積收縮特性及機械性質等之影響研究。
本研究也利用小角度X-ray散射儀(SAXS)測量不飽和聚酯(UP)及乙烯基酯(VER)之稀薄苯乙烯(St)溶液之散射強度，再根據Guinier Law計算不同UP及乙烯基酯(VER)之環動半徑(Radius of Gyration)，可用於St/UP(或VER)/MMT三成份系統，瞭解UP(或 VER)分子擴散至蒙特納石黏土(MMT)層間之難易程度。

The effects of four additives, including (1) nano- scale and submicron-scale core-shell rubber additive,(2) inorganic silica gel/organic polymer core-shell particle, (3) organic montmorillonite clay, on the cure kinetics, glass transition temperatures, cured sample morphology, volume shrinkage characteristics and mechanical properties of the Styrene(St)/ Unsaturated polyester (or Vinyl ester resin)/ additives ternary systems and Epoxy/curing agent /additive ternary systems after the cure have been investigated.
The experimental results have been explained by integrated measurements combining phase characteristic of the St/VER/additive ternary system and Epoxy/curing agent /additive ternary systems before the cure, final cure conversion, glass transition temperature, SAXS and WAXS analysis, cured sample morphology and Mechanical properties.
Also the scattering intensity of vinyl ester resin (VER) and unsaturated polyester (UP) with different structure in dilute styrene solution was measured by the method of small angle X-ray scattering (SAXS), and the radius of gyration of VER and the UP molecule can then be calculated by using the Guinier law.

摘要 I
Abstract II
目錄 III
圖目錄 VII
表目錄 X
第1章 緒論 1
1-1 不飽和聚酯(UP) 1
1-1-1 環氧樹脂 (Epoxy Resin )[2-7] 2
1-1-2 環氧樹脂之硬化劑[2, 3] 6
1-1-3 環氧樹脂硬化之流變行為[7] 9
1-2 乙烯基酯樹脂(Vinyl Ester Resin , VER) 10
1-3 增韌劑 11
1-4 抗收縮劑 12
1-5 蒙特納石黏土及其高分子奈米複合材料 14
1-6 研究範疇 15
第2章 文獻回顧 17
2-1 自由基聚合反應 17
2-2 不飽和聚酯(UP)樹脂之合成 20
2-3 不飽和聚酯(UP)樹脂與苯乙烯(ST)之交聯共聚合反應 21
2-4 苯乙烯/不飽和聚酯(UP) /抗收縮劑(LPA)三成份系統之相溶性研究 24
2-5 低收縮不飽和聚酯樹脂之抗收縮補償機構 25
2-6 低收縮不飽和聚酯樹脂系統聚合固化後微觀結構之研究 27
2-7 抗收縮劑對UP樹脂固化後體積收縮影響之研究 29
2-8 不飽和聚酯硬化後的機械性質研究 31
2-9 核殼性橡膠增韌劑 33
2-10 蒙特納石黏土-不飽和聚酯高分子奈米複合材料研究 36
2-11 可逆加成-斷裂鏈轉移聚合法(RAFT) [76-81] 40
第3章 實驗方法與設備 42
3-1 實驗原料 42
3-1-1 不飽和聚酯樹脂、環氧樹脂與乙烯基酯樹脂 42
3-1-2 特用添加劑 45
3-1-2-1 核殼型橡膠(Core-Shell Rubber，CSR) 45
3-1-2-2 無機/有機核殼型顆粒(Core-Shell particle, CSP) 46
3-1-2-3 蒙特納石黏土(Montmorillonite Clay, MMT) 52
3-1-3 實驗藥品 52
3-2 實驗儀器 55
3-3 實驗步驟 58
3-3-1 MMT clay之鈉活性化處理[33] 58
3-3-2 Silane-treated MMT之製備[33] 58
3-3-3 Alkylammonium-MMT (AMMT)之製備 59
3-3-4 Silane-treated AMMT之製備 59
3-3-5 有機化改質MMT鑑定 61
3-3-5-1 FTIR定量分析 61
3-3-5-2 WAXS 散射實驗 63
3-3-6 Neat St/UP(VER) 溶液與固化試片製備 64
3-3-7 St/UP(VER)/特用添加劑之三成分溶液與固化試片製備 66
3-3-8 Epoxy/DDM 雙成份溶液製備 68
3-3-9 Epoxy/DDM/CSP三成份溶液與固化試片製備 69
3-3-10 Epoxy/DDM/CSR三成份系統溶液與固化試片製備 71
3-3-11 體積變化量測-密度法 72
3-3-12 微分掃描熱卡計(DSC)樣品製備 72
3-3-13 動態機械分析儀試片製備 73
3-3-14 掃描式電子顯微鏡(SEM)觀測樣品製備 74
3-3-15 穿透式電子顯微鏡(TEM)觀測樣品製備 74
3-3-16 拉伸測試 76
3-3-17 耐衝擊測試 77
3-3-18 波松比測試 78
3-3-19 破壞韌性測試 79
3-3-20 破壞能量 79
3-3-21 利用SAXS測定不飽和聚酯及乙烯基酯之環動半徑 80
3-4 性質測試原理與分析 82
3-4-1 DSC熱分析 82
3-4-2 DMA理論[86] 84
3-4-3 小角度X-ray散射(SAXS)之相關理論 86
3-4-3-1 X-ray簡介[39, 87, 88] 86
3-4-3-2 X光的產生 86
3-4-3-3 X光與中子散射 88
3-4-4 SAXS測定高分子稀薄溶液以求算高分子環動半徑之理論 90
3-4-4-1 Guinier Law 90
3-4-5 以穿透因子(transmission factor)校正X光散射強度及溶劑背景散射 強度之消除 95
第4章 結果與討論 98
4-1 以小角度X光散射法高分子之環動半徑(Rg)測定 98
4-2 有機化改質之MMT鑑定 120
4-2-1 FTIR定量分析 120
4-2-1-1 Silane-treated MMT 120
4-2-1-2 AMMT 124
4-2-1-3 Silane-treated AMMT 129
4-2-2 有機化MMT之WAXS鑑定 130
4-3 St/UP (or VER)/Additive與Epoxy/DDM/Additive之三成份系統相溶性研 究 132
4-3-1 添加核殼型橡膠(CSR)之三成份系統 132
4-3-2 添加無機/有機核殼顆粒(CSP)之三成份系統 137
4-3-3 添加Silane-treated MMT之三成份系統 138
4-4 SEM微觀型態結構 140
4-4-1 Neat Epoxy/DDM雙成份系統 140
4-4-2 Neat St/VER 雙成分系統 146
4-4-3 St/VER/Si-PMA-15 三成份系統 151
4-4-4 Epoxy/DDM/Si-PMA-15nm 155
4-4-5 Epoxy/DDM/MA-Gx-30 三成份系統 159
4-5 TEM微觀型態結構 165
4-5-1 St/VER/Si-PMA-15 三成份系統 165
4-5-2 Epoxy/DDM/Si-PMA-15 三成份系統 170
4-5-3 Epoxy/DDM/MA-Gx-30 三成份系統 175
4-5-4 St/UP(MA-PG)/Silane-treated MMT 三成份系統 181
4-5-5 St/VER/Silane-treated AMMT 三成份系統 186
4-6 固化反應動力研究 187
4-6-1 Neat Epoxy/DDM 雙成份系統 187
4-6-2 Neat St/VER 雙成份系統 193
4-7 玻璃轉移溫度測定 198
4-7-1 Neat Epoxy/DDM 雙成份系統 198
4-7-2 Neat St/VER 雙成份系統 200
4-7-3 St/VER/Si-PMA-15 三成份系統 202
4-7-4 Epoxy/DDM/MA-Gx-30 三成份系統 204
4-7-4-1 Epoxy/DDM/MA-G0-30 三成分系統 204
4-7-4-2 Epoxy/DDM/MA-G1-30 三成份系統 206
4-7-4-3 Epoxy/DDM/MA-G2-30 三成份系統 208
4-8 體積收縮特性 212
4-8-1 St/MA-PG/AMMT 三成份系統 212
4-8-2 St/MA-PG/Silane treated MMT 三成份系統 213
4-9 機械性質研究 215
4-9-1 Neat Epoxy/DDM 雙成份系統之機械性質測試 215
4-9-1-1 Neat Epoxy/DDM雙成份系之耐衝擊強度 215
4-9-1-2 Neat Epoxy/DDM雙成份系之破壞韌性 216
4-9-1-3 Neat Epoxy/DDM雙成份系之破壞能量 217
4-9-1-4 Neat Epoxy/DDM雙成份系之楊氏模數 218
4-9-1-5 Neat Epoxy/DDM雙成份系之抗張強度 219
4-9-2 Neat St/VER 雙成份系統之機械性質測試 220
4-9-2-1 Neat St/VER 雙成分系之耐衝擊強度 220
4-9-2-2 Neat St/VER 雙成分系之楊氏模數 221
4-9-2-3 Neat St/VER 雙成分系之抗張強度 221
4-9-3 Epoxy/DDM/MA-Gx-30 三成份系統之機械性質測試 222
4-9-3-1 Epoxy/DDM/MA-Gx-30 三成份系之耐衝擊強度 222
4-9-3-2 Epoxy/DDM/MA-Gx-30 三成份系之破壞韌性 223
4-9-3-3 Epoxy/DDM/MA-Gx-30 三成份系之破壞能量 224
4-9-3-4 Epoxy/DDM/MA-Gx-30 三成分系之楊氏模數 225
4-9-3-5 Epoxy/DDM/MA-Gx-30 三成分系之抗張強度 226
4-9-4 St/VER/Si-PMA-15 三成份系統之機械性質測試 227
4-9-4-1 St/VER/Si-PMA-15 三成份系之耐衝擊強度 227
4-9-4-2 St/VER/Si-PMA-15 三成份系之楊氏模數 228
4-9-4-3 St/VER/Si-PMA-15 三成份系之抗張強度 229
第5章 結論 230

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