臺灣博碩士論文加值系統

本文探討次微米級核殼型橡膠(CSR)、奈米級無機二氧化矽顆粒(SNP)和熱還原氧化石墨烯(TRGO)三種特用添加劑對苯乙烯(St)/乙烯基酯(VER)/特用添加劑三成份系統其聚合固化之微觀型態結構、抗體積收縮及機械性質之影響。
奈米級無機二氧化矽顆粒其表面經由帶C=C雙鍵的矽烷MPS改質而得，次微米級核殼型橡膠(CSR)其核心為聚丙烯酸正丁酯(PBA)，而外殼主要為聚甲基丙烯酸甲酯(PMMA)，並且用15 mole %帶有環氧基團之甲基丙烯酸環丙氧酯(GMA)改質外殼。氧化石墨則藉由帶有C=C雙鍵之3-(甲基丙烯醯氧)丙基三甲氧基矽烷(γ-MPS)改質親水性氧化石墨獲得官能基化氧化石墨。
上述三種特用添加劑對St/VER/特用添加劑三成份系統在反應前之相容性，固化樣品之SEM及TEM微觀結構、體積收縮及機械性質，將於文中探討之其聚合物之實驗結果。

The effects of the submicron-scale core–shell rubber (CSR), nano-scale silane-grafted silica nanoparticles (SNP) and thermally reduced graphene oxide as special additives on volume shrinkage characteristics and mechanical properties of the styrene (St)/vinyl ester resin(VER)/special additive ternary systems cured at 120 ℃ and post cured at 150 ℃have been investigated.
The SNP with a diameter of 15 nm was synthesized by size-controllable hydrolysis of elemental silicon, followed by the surface treatment of 3-methacryloxypropyltrimethoxysilane (γ-MPS) to obtain the MPS-silica. The CSRs were synthesized by two-stage soapless emulsion polymerizations, where the soft core was made from rubbery poly(n-butyl acrylate), and the hard shell was made from 85 mole% of methyl methacrylate, 15mol% glycidyl methacrylate, and 1mole% of ethylene glycol dimethacrylate as the crosslinking agent.
The experimental results are explained by an integrated approach of measurements of the static phase characteristics of a St/VER/special additive system, the cured sample morphology with SEM, TEM, and mechanical properties.

摘要 I
Abstract II
第一章 緒論 1
1-1不飽和聚酯(UP) 1
1-2乙烯基酯樹脂(Vinyl Ester Resin , VER) 2
1-3增韌劑 3
1-4抗收縮劑 5
1-5蒙特納石黏土及其高分子奈米複合材料 6
1-6石墨烯/高分子奈米複合材料 7
1-7矽烷偶合劑改質氧化石墨/熱脫層氧化石墨烯之奈米高分子複合材料 14
1-8研究範疇 15
第二章 文獻回顧 16
2-1自由基聚合反應 16
2-2不飽和聚酯(UP)樹脂之合成 19
2-3不飽和聚酯(UP)樹脂與苯乙烯(St)之交聯共聚合反應 20
2-4苯乙烯(St) /不飽和聚酯(UP) /抗收縮劑(LPA)三成份系統之相溶性研究 23
2-5低收縮不飽和聚酯樹脂之抗收縮補償機構 24
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 26
2-7抗收縮劑對UP樹脂固化後體積收縮影響之研究 28
2-8不飽和聚酯硬化後的機械性質研究 30
2-9核殼性橡膠增韌劑 32
2-10蒙特納石黏土-不飽和聚酯高分子奈米複合材料研究 35
2-11石墨烯/高分子奈米複合材料之研究 38
2-12氧化石墨(GO)及熱還原氧化石墨(TRGO)的製備 39
2-13烷氧基矽烷偶合劑改質之氧化石墨(Silane-GO)及熱還原氧化石墨烯(Silane-TRGO) 42
第三章 實驗方法與設備 44
3-1實驗原料 44
3-1-1環氧樹脂與乙烯基酯樹脂 44
3-1-2特用添加劑 47
3-1-2-1通用型核殼型橡膠(General Purpose Core-Shell Rubber，gp-CSR) 47
3-1-2-1矽烷偶合劑接枝奈米級無機二氧化矽顆粒(nano-scale silane-grafted silica nanoparticles，SNP) 48
3-1-3實驗藥品 49
3-2實驗儀器 52
3-3實驗步驟 55
3-3-1 熱還原氧化石墨烯製備(39, 88, 88a) 55
3-3-2 烷氧基矽烷偶合劑改質氧化石墨(Silane-GO) 56
3-3-3 WAXS 散射實驗 57
3-3-4 FTIR定性分析 57
3-3-5 Neat St/UP(VER) 溶液之固化試片製備 58
3-3-6 St/UP(VER)/additive之三成份溶液之固化試片製備 60
3-3-7體積變化量測-密度法 62
3-3-8 St/VER(n=2)/additive之三成分系統相分離特性 63
3-3-9拉伸測試 64
3-3-10耐衝擊測試 64
3-3-11波松比測試 65
3-3-12破壞韌性測試 66
3-3-13破壞能量 67
3-3-14掃描式電子顯微鏡(SEM)觀測樣品製備 67
3-3-15穿透式電子顯微鏡(TEM)觀測樣品製備[88a] 67
第四章 結果與討論 69
4-1 St/VER(n=2)/Additive之三成份系統未反應前之相溶性研究 69
4-1-1 CSR(BA/MMA-EGDMA-GMA(500nm))之三成份系統 69
4-1-2 Silane改質奈米級二氧化矽顆粒 (MPS-SiO2)之三成份系統 70
4-2 Takayanagi 機械模式 71
4-3 St/VER(n=2)/CSR(BA/MMA-EGDMA-GMA(15)(500nm))之MR=2/1三成份系統 73
4-3-1 SEM微觀型態結構 73
4-3-2 TEM微觀型態結構 76
4-3-3體積收縮特性 82
4-3-4機械性質研究 84
4-3-4-1耐衝擊強度 84
4-3-4-2楊氏模數 85
4-3-4-3抗張強度 87
4-3-4-4斷裂拉伸率 88
4-4 St/VER(n=2)/SNP(MPS-SiO2)之MR=2/1三成份系統 90
4-4-1 SEM微觀型態結構 90
4-4-2 TEM微觀型態結構 93
4-4-3體積收縮特性 98
4-4-4 機械性質研究 100
4-4-4-1耐衝擊強度 100
4-4-4-2楊氏模數 102
4-4-4-3抗張強度 104
4-4-4-4斷裂拉伸率 106
4-5 St/VER(n=2)/CSR(BA/MMA-EGDMA-GMA(15)(500nm)) /SNP(MPS-SiO2)之MR=2/1四成份系統 108
4-5-1 SEM微觀型態結構 108
4-5-2 TEM微觀型態結構 111
4-5-3體積收縮特性 115
4-5-4機械性質研究 117
4-5-4-1耐衝擊強度 117
4-5-4-2楊氏模數 119
4-5-4-3抗張強度 121
4-5-4-4斷裂拉伸率 123
4-5-5總結 125
4-6熱還原氧化石墨烯(TRGO) 126
4-7烷氧基矽烷偶合劑改質之氧化石墨(Silane-GO) 131
4-8 St/VER(n=2)/TRGO之MR=2/1三成份系統 136
4-8-1 SEM微觀型態結構 136
4-8-2 TEM微觀型態結構 139
4-8-3體積收縮特性 144
4-8-4機械性質研究 146
4-8-4-1耐衝擊強度 146
4-8-4-2楊氏模數 147
4-8-4-3抗張強度 149
4-8-4-4斷裂拉伸率 150
第五章 結論 152
第六章 建議與未來工作 156
第七章 參考文獻 157
第八章 附錄 163

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