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研究生： 黃姵瑜
Pei-Yu Huang
論文名稱： 由元素矽水解法合成無機二氧化矽奈米顆粒及探討核殼型橡膠、無機二氧化矽顆粒、矽烷接枝及高分子接枝之氧化石墨烯及熱脫層氧化石墨烯對乙烯基酯樹脂之聚合固化反應動力及玻璃轉移溫度之影響
Synthesis of nano-scale colloidal silica from elemental silicon by hydrolysis, and effects of core-shell rubber, inorganic silica nanoparticles, silane-grafted and polymer-grafted graphene oxide and thermally reduced graphene oxide on the cure kinetics and glass transition temperatures for vinyl ester resins
指導教授： 黃延吉
Yan-Jyi Huang
口試委員: 邱文英
Wen-Yen Chiu
陳崇賢
Chorng-Shyan Chern
學位類別： 碩士
Master
系所名稱： 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年： 2017
畢業學年度： 105
語文別： 中文
論文頁數： 208
中文關鍵詞： 核殼型橡膠 、二氧化矽奈米顆粒 、乙烯基酯樹脂 、聚合固化反應動力 、微分掃描熱分析儀 、傅立葉紅外光分析儀 、氧化石墨烯 、熱脫層氧化石墨烯 、玻璃轉移溫度 、動態機械分析儀
外文關鍵詞： Core-Shell Rubber, silica nanoparticle, vinyl ester resin, curing kinetics, DSC, FTIR, graphene oxide, thermally reduced graphene oxide, glass transition, DMA
相關次數： 點閱：527  下載：6 
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    • 本文利用元素矽水解法合成無機二氧化矽奈米顆粒，並可以有效控制其顆粒大小，本文亦探討另外五種特用添加劑，分別為 (1)奈米級及次微米級核殼型橡膠 (2)氧化石墨烯 (3)不同熱脫層溫度之熱脫層氧化石墨烯 (4)高分子接枝之氧化石墨烯 (5)矽烷接枝之氧化石墨烯，其對苯乙烯(St)/乙烯基酯樹脂(VER)/特用添加劑三成份系統之聚合固化反應動力、玻璃轉移溫度及X光散射特性之影響。

    吾人利用拉曼光譜儀鑑定 (1)官能基化氧化石墨烯 (2)官能基化之不同熱脫層溫度之脫層石墨烯 (3)高分子接枝之氧化石墨烯 (4)矽烷接枝之氧化石墨烯之化學結構。

    此外，吾人亦使用差式掃描卡計(DSC)及傅立葉轉化紅外線光譜儀(FTIR)測量St/VER雙成份系統與St/VER/特用添加劑之三成份系統在聚合固化過程中的反應動力。最後根據Takayanagi機械模式，苯乙烯/乙烯基酯樹脂/特用添加劑聚合固化系統其在每一相區的玻璃轉移溫度，吾人亦使用動態機械分析儀(DMA)測定之。

    In this study, silica nanoparticles(SNP) with a diameter ranging from15 nm to 60 nm were synthesized by size-controllable hydrolysis of elemental silicon. The effects of five other additives, including (1) nano-scale and submicron-scale core-shell rubber additive , (2) graphene oxide, and (3) thermally reduced graphene oxide, (4) polymer-grafted graphene oxide (5) silane-grafted graphene oxide, on the cure kinetics, glass transition temperature and X-ray scattering characteristics for the styrene(St)/vinyl ester resin(VER)/special additives ternary systems after the cure have also been investigated.
    In addition, the chemical structures of functionalized graphene oxide (GO) and functionalized thermally reduced graphene (TRGO) and polymer-grafted graphene oxide and silane-grafted graphene oxide were also characterized by Raman Spectroscopy (RS).
    Moreover, the reaction kinetics for the St/VER/special additive ternary or tetra system during the cure was measured by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). Finally, based on the Takayanagi mechanical models, the glass transition temperature in each region of the cured samples for St/VER/special additive ternary system has been measured by dynamic mechanical analysis (DMA).

    摘 要 I Abstract II 致 謝 III 目錄 IV 圖目錄 IX 表目錄 XIX 第一章 緒論 1 1-1 二氧化矽 1 1-2 不飽和聚酯樹脂 (UP Resin) 2 1-3 環氧樹脂 (Epoxy Resin ) 3 1-4 乙烯基酯樹脂 (Vinyl Ester Resin, VER) 6 1-5 增韌劑 (Toughener) 7 1-6 抗體積收縮劑(Low-Profile Additives, LPA) 9 1-7 石墨烯/高分子奈米複合材料 10 1-8 研究範疇 16 第二章 文獻回顧 17 2-1 二氧化矽 17 2-1-1 二氧化矽製備 18 2-2 自由基聚合反應 20 2-3 不飽和聚酯樹脂(UP)合成 22 2-4 不飽和聚酯樹脂(UP)和苯乙烯(St)之交聯共聚合反應 23 2-5 苯乙烯/不飽和聚酯/抗收縮劑三成分系統之相容性研究 25 2-6 不飽聚酯(UP)樹脂之聚合固化後微觀結構之研究 26 2-7 不飽和聚酯(UP)樹脂之抗收縮補償機制 27 2-8 不飽和聚酯樹脂之反應動力學模式之研究 29 2-9 核殼型橡膠增韌劑 33 2-10 不飽和聚酯樹脂玻璃轉移溫度之研究 35 2-11 石墨烯/高分子奈米複合材料 36 2-12 氧化石墨(GO)及熱還原氧化石墨(TRGO)的製備 37 2-13 苯乙烯(St)/乙烯基酯樹脂(VER)之反應動力 38 第三章 實驗方法與設備 39 3-1 實驗原料 39 3-1-1 二氧化矽顆粒(Silica,SiO2) 39 3-1-2 環氧樹脂 40 3-1-3 乙烯基酯樹脂 41 3-1-4 通用型次微米級核殼型橡膠(General Purpose Core-Shell Rubber, gp-CSR) 42 3-1-5 通用型奈米級核殼型橡膠(General Purpose Core-Shell Rubber, gp-CSR) 43 3-1-6 氧化石墨(Graphite Oxide, GO)與熱還原氧化石墨(Thermally Reduced Graphite Oxide, TRGO) 44 3-1-7 高分子接枝之氧化石墨烯(Polymer-grafted graphene oxide, GO-polymer) 45 3-1-8 矽烷接枝之氧化石墨烯(Silane-grafted graphene oxide , sg-GO) 46 3-1-9 實驗藥品 47 3-2 實驗儀器 50 3-3 實驗步驟 52 3-3-1 元素矽水解法合成二氧化矽(Silica) 52 3-3-2 活化二氧化矽顆粒 54 3-3-3 未反應之MPS Silane-treated SiO2製備 55 3-3-4 反應之MPS Silane-treated SiO2製備 55 3-3-5 St/VER雙成份系統溶液製備 56 3-3-6 St/VER(n=2)/特用添加劑三成份系統溶液製備 56 3-3-7 動態機械分析儀(DMA)固化試片製作 57 3-3-8 微分掃描卡計(DSC)反應動力測定 58 3-3-9 傅立葉紅外線光譜儀(FTIR)校正曲線測定 58 3-3-10 傅立葉紅外線光譜儀(FTIR)固態之樣品製備與測定 59 3-3-11 傅立葉紅外線光譜儀(FTIR)反應動力測定 59 3-3-12 拉曼光譜儀(RS)測定樣品製備 60 3-4 性質測定與分析方法 61 3-4-1 拉曼光譜儀(RS)分析 61 3-4-2 微分掃描卡計(DSC)熱分析 62 3-4-3 St/VER系統之微分掃描卡計(DSC)數據校正 63 3-4-4 動態機械分析儀(DMA)理論 64 3-4-5 傅立葉紅外線光譜儀(FTIR)測定反應動力之理論與分析 65 3-4-6 St/VER system 反應動力分析 66 第四章 結果與討論 69 4-1 二氧化矽的合成及鑑定 69 4-1-1 元素矽水解法合成膠體二氧化矽奈米顆粒 69 4-1-2 活化前後二氧化矽顆粒之FTIR鑑定 74 4-2 MPS型Silane改質Silica鑑定 81 4-2-1 FTIR定量分析 82 4-2-1-1 Silane校正曲線測定 82 4-2-1-2 未反應之MPS 型Silane treated SiO2 84 4-2-1-3 反應後Silane(MPS)-treated SiO2 87 4-2-2 MPS Silane treated SiO2接枝率 90 4-3 拉曼光譜儀(Raman Spectroscope, RS)測定 93 4-4 DSC反應動力 97 4-4-1 不同St對VER之C=C雙鍵莫耳比(MR)之St/VER(n=2)雙成份系統 97 4-4-2 St/VER(n=2)/氧化石墨烯(GO)三成分系統 102 4-4-3 St/VER(n=2)/熱還原氧化石墨烯(TRGO)三成分系統 108 4-4-3-1 TRGO-400C 108 4-4-3-2 TRGO-700C 112 4-4-3-3 TRGO-1050C 116 4-4-4 St/VER(n=2)/高分子接枝之氧化石墨烯(GO-G10)三成分系統 120 4-4-5 St/VER(n=2)/高分子接枝之氧化石墨烯(GO-G20)三成分系統 126 4-4-6 St/VER(n=2)/高接枝密度矽烷偶合劑改質之氧化石墨烯(HD-sg-GO)三成分系統 132 4-5 玻璃轉移溫度(Tg)測定 137 4-5-1 St/VER(n=2)/氧化石墨烯(GO)三成分系統 137 4-5-2 St/VER(n=2)/熱還原氧化石墨烯(TRGO)三成分系統 140 4-5-2-1 TRGO-400C 140 4-5-2-2 TRGO-700C 143 4-5-2-3 TRGO-1050C 146 4-5-3 St/VER(n=2)/高分子接枝之氧化石墨烯(GO-G10)三成分系統 149 4-5-4 St/VER(n=2)/高分子接枝之氧化石墨烯(GO-G20)三成分系統 152 4-5-5 St/VER(n=2)/高接枝密度矽烷偶合劑改質之氧化石墨烯(HD-sg-GO)三成分系統 155 4-6 FTIR鑑定 158 4-7 FTIR校正曲線測定 159 4-8 FTIR反應動力 166 4-8-1 St/VER(n=2)於莫耳比MR=2/1下之120℃聚合固化反應之雙成份系統(TFC內有加墊片) 166 4-8-2 St/VER(n=2)於莫耳比MR=2/1下之120℃聚合固化反應之雙成份系統(TFC內無加墊片) 169 第五章 結論 172 第六章 建議與未來工作 178 第七章 參考文獻 179

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