含硫與芳香環之高折射率環氧樹脂的合成與硬化後物性研究
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(2) 含硫與芳香環之高折射率環氧樹脂的合成與硬化後物 性研究 Synthesis and Physical Properties of Sulfur and Aromatic Ring-Containing Epoxy Resins with High Refractive Index. 研 究 生：黃俊豪. Student：Chun-Hao Huang. 指導教授：林木獅 博士. Advisor：Dr. Mu-Shin Lin. 國立交通大學 應用化學研究所 碩士論文 A Thesis Submitted to Department of Applied Chemistry College of Science National Chaio Tung University in partial Fulfillment of the Requirements for the Degree of Master of Science in Applied Chemistry July 2004 Hisnchu,Taiwan,Republic of China. 中華民國九十三年七月.
(3) Synthesis and Physical Properties of Sulfur and Aromatic Ring-Containing Epoxy Resins with High Refractive Index. Student：Chun-Hao Huang. Advisor：Dr. Mu-Shin Lin. Instituted of Applied Chemistry National Chioa Tung University. Abstract. This research is focused on syntheses of three novel difunctional epoxies containing sulfur and benzene ring.:EpoxyⅠ｛Diglycidyl ether of 4,4'-thiodiphenol｝, EpoxyⅡ｛Diglycidyl ether of 4,4'-thiobis(2-tert-butyl -5-methylphenol)｝, EpoxyⅢ｛Diglycidyl thioether of 4,4'-thiodibenzenethiol｝. The properties of the epoxies which we synthesized were compared with that of commercially available 830LVP epoxy. These epoxies were further cured with two anhydrides and two thiols. Optical properties including refractive index and ultraviolet/visible spectrum were characterized. Thermal properties of these epoxy resins were also studied by Thermogravimetric Analyzer (TGA),Differential i.
(4) Scanning Calorimetry (DSC),and Thermal Mechanical Analyzer (TMA). Experimental results showed that EpoxyⅢ / 4,4'-thiodibenzenethiol (CAⅣ).Indicate the highest refractive index of 1.7328.Becase this system contains the highest percentage of sulfur and aromatic ring carbons. All samples showed good transparency of 80% to 90%.In addition TGA thermograms indicated good thermal stabilities for all these samples. The unset of 5% weight loss occurred at temperatures higher than 270℃.. ii.
(5) 含硫與芳香環之高折射率環氧樹脂的合成與硬化後物 性研究. 研究生：黃俊豪. 指導教授：林木獅 博士. 交通大學應用化學所. 摘要. 本研究合成三種不同含硫量的環氧樹脂：即EpoxyⅠ｛Diglycidyl ether of 4,4'-thiodiphenol｝, EpoxyⅡ｛Diglycidyl ether of 4,4'-thiobis(2tert-butyl-5-methylphenol)｝, EpoxyⅢ｛Diglycidyl thioether of 4,4'-thiodibenzenethiol｝ ，並選用商品環氧樹脂830LVP做為比較組，分別與兩 種酸酐及兩種硫醇硬化劑硬化，可得到12組材料，由這些材料探討含 硫量以及含芳香環比例對於折射率的影響，並討論光穿透度，即測量 以光波長為589nm光的折射率以及在可見光/紫外光區域的穿透性。 鑑定分析，以FT-IR研究其交聯行為，以動態DSC探討交聯動力 學，以TGA，TMA，測量熱裂解以及熱機械性質。 EpoxyⅢ/4,4'-thiodibenzenethiol(CAⅣ)含硫量以及含芳香環的比 iii.
(6) 例皆為所有配方中較高的，擁有最高的折射率(1.7328)，本論文的所 有系統在光波長為400nm以上的光穿透度皆可以達到80%至90%。 TGA結果顯示，本論文配方系統中皆有良好的抗熱性，均因為含有雙 苯環的結構，在5%的重量損失溫度都在270℃以上。. iv.
(7) 誌謝. 本論文得以完成，完全承蒙於恩師 林木獅博士兩年來的細心指 導，在此致上最崇高的敬意。 感謝口試委員 李選能教授、 黃華宗教授能在百忙之中費心審查 論文，提供作學問的金玉良言。. 感謝學長 天哥給予我實驗上諸多的指導與幫忙，在遇到挫敗時給 我方向。謝謝學長王Sir在實驗上給予我許多寶貴的意見。另外謝謝學長 阿仁、志浩、布萊恩給予我實驗上寶貴的經驗及意見。當然還要謝謝學 長 小張在課業實驗以及生活上給予我的幫助。 感謝學長 小南、小傑以及實驗室共度兩年的夥伴們 小蘇、阿澍， 陪著我在實驗之餘的 NBA 廝殺，當然常常被我電也帶給我莫名的成就 感，阿澍想在我面前灌藍在練一萬年，小蘇灌籃秀喔，小傑好好的練啦! 當然我唯一的學弟 毓棟也要好好的謝謝一番，感謝你都最早來開門讓 學長我可以無後顧之憂的睡，還有在實驗上給予我的協助，雖然常常做 不出來，不過在我心中你是最好的學弟。.
(8) 這篇論文得來不易，特別要感謝我的麻機 賽鳥在實驗之餘帶給我 歡笑與樂趣，還有翔暘、少爺、火龍、凱芳、等等謝謝你們一路上的陪 伴，還有小 Ki 回家後我會好好陪你的，當然還要感謝我那可愛的女朋 友一路上給予我鼓勵以及陪伴，體諒我讓我毫無後顧之憂。. 最後我要感謝我的父母謝謝你們在這一路上的支持，在我的生活及. 精神上給予我最大的支持與鼓舞，讓我可以沒有後顧之憂的完成我的 學業。茲這得來不易的成果與你們分享。.
(9) 目錄 頁次 英文摘要..................................................................................................i 中文摘要……………………………………………………………….iii 目錄……………………………………………………………………..v 表目錄…………………………………………………………………..xi 圖目錄…………………………………………………………………xiii. 第一章 緒論…………………………………………………………….1 1-1 高折射環氧樹脂的應用…………………………………………..1 1-1-1 作為 LED 的封裝材料………………………………………...1 1-1-2 光學接著劑（Optical Adhesive）…………………………….3 1-1-3 光學鏡片……………………………………………………….6 1-2 關於環氧樹脂的介紹與原理……………………………………...7 1-2-1 環氧樹脂的簡介……………………………………………….7 1-2-2 環氧樹脂硬化反應機構……………………………………….9 1-2-2-1 常見的環氧樹脂硬化劑……………………………………9 1-2-2-2 環氧樹脂與酸酐類硬化劑…………………………………9 1-2-2-3 環氧樹脂與硫醇類類硬化劑………………......................11. v.
(10) 1-2-3 環氧樹脂硬化之流變行為與動力學………………………...13 1-3 高折射率高分子材料簡介………………………………………16 1-3-1 高分子折射率………………………………………………...16 1-3-2 高折射率有機材料…………………………………………...17 1-4 文獻回顧…………………………………………………………19 1-4-1 含硫光學樹脂………………………………………………...19 1-4-1-1 含硫環氧樹脂……………………………………………..19 1-4-1-2 高折射率環硫型光學樹脂………………………………..20 1-4-2 其他商業上以硫原子提高高分子折射率的文獻分析……...21 1-4-3 使用複合材料的方式提高折射率的文獻分析………...........23 1-4-4 由高分子結構著手提高折射率的文獻分析…………….......24 1-5 研究動機………………………………………………………….27. 第二章 實驗部份………………………………………………............29 2-1 實驗材料………………………………………………………….29 2-1-1 環氧樹脂系統...........................................................................29 2-1-2 其他實驗相關藥品…………………………………………...32 2-2 實驗儀器與設備…………………………………………………..34 2-3 實驗流程………………………………………………………….36. vi.
(11) 2-4 合成環氧樹脂單體………………………………………………..37 2-5 環氧當量滴定…………………………………………………….41 2-6 合成化合物鑑定………………………………………………….43 2-6-1 1H 核磁共振光譜……………………………………………..43 2-6-2 13C 核磁共振光譜…………………………………………….43 2-6-3 紅外線光譜分析……………………………………………...43 2-7 交聯行為分析.................................................................................43 2-7-1 交聯配方……………………………………………………...43 2-7-1-1 Epoxy/CAⅠSystem………………………………………..43 2-7-1-2 Epoxy/CAⅡSystem………………………………………..45 2-7-1-3 Epoxy/CAⅢSystem………………………………………..47 2-7-1-4 Epoxy/CAⅣSystem………………………………………..48 2-7-2 動態 DSC 分析………………………………………………..49 2-7-3 交聯過程的 FT-IR 分析………………………………………50 2-8 試片製作………………………………………………………….50 2-8-1 熱分析試片…………………………………………………...50 2-8-2 UV/VIS Transmission 測量試片的製備………………………51 2-8-2-1 石英基材的清洗…………………………………………..51 2-8-2-2 UV/VIS Transmission 試片製作…………………………..51. vii.
(12) 2-8-3 折射率測量試片的製備(film)………………………………..52 2-8-3-1 環氧樹脂與 CAⅠ、CAⅡ、CAⅣ………………………52 2-8-3-2 環氧樹脂與 CAⅢ................................................................52 2-9 交聯後材料性質測試…………………………………………….53 2-9-1 熱重量分析儀(TGA)分析…………………………………….53 2-9-2 熱膨脹係數的測試(TMA)……………………………………53 2-9-3 微差熱掃描卡計(DSC)……………………………………….53 2-9-4 凝膠分率之測試（Gel fraction）……………………………54 2-9-5 折射率測試…………………………………………………...54 2-9-6 透明度測試(UV/VIS Transmission)………………………….54. 第三章 結果與討論…………………………………………………....55 3-1 合成環氧樹脂單體之鑑定與分析……………………………….55 3-1-1 EpoxyⅠ………………………………………………………..55 3-1-1-1 合成流程..............................................................................55 3-1-1-2 結構鑑定分析……………………………………………..55 3-1-1-3 結果整理……………………………………………………56 3-1-2 EpoxyⅡ………………………………………………………..57 3-1-2-1 合成流程…………………………………………………..57 3-1-2-2 結構鑑定分析……………………………………………..57 viii.
(13) 3-1-2-3 結果整理……………………………………………………58 3-1-3 EpoxyⅢ......................................................................................59 3-1-3-1 合成流程…………………………………………………..59 3-1-3-2 結構鑑定分析………………………………………………59 3-1-3-3 結果整理................................................................................60 3-2 環氧樹脂的交聯行為探討.............................................................61 3-2-1 決定硬化條件(動態 DSC 分析)………………………………61 3-2-1-1 環氧樹脂與酸酐類硬化劑 (CAⅠ，CAⅡ)………………61 3-2-1-2 環氧樹脂與硫醇類硬化劑 (CAⅢ，CAⅣ)………………63 3-2-2 由動態 DSC 試算反應活化能..................................................66 3-2-3 紅外線光譜分析.......................................................................67 3-2-3-1 EpoxyⅠ/CAⅠ之反應 FT-IR 分析.......................................68 3-2-3-2 EpoxyⅠ/CAⅡ之反應 FT-IR 分析.......................................68 3-2-3-3 EpoxyⅠ/CAⅢ之反應 FT-IR 分析………………………...69 3-2-3-4 EpoxyⅠ/CAⅣ之反應 FT-IR 分析.......................................69 3-2-4 凝膠分率測試………………………………………………...70 3-3 交聯產物光學性質分析.................................................................72 3-3-1 折射率分析...............................................................................72 3-3-1-1 相同硬化劑不同環氧樹脂的折射率分析比較..................72. ix.
(14) 3-3-1-2 相同環氧樹脂不同硬化劑的折射率分析比較..................74 3-3-2 光穿透度探討...........................................................................75 3-3-2-1 相同環氧樹脂不同硬化劑的比較......................................75 3-3-2-2 相同硬化劑不同環氧樹脂的比較………………………..76 3-4 交聯產物熱性質分析………………………………………….....78 3-4-1 玻璃轉移溫度...........................................................................78 3-4-1-1 不同硬化劑的比較..............................................................78 3-4-1-2 不同環氧樹脂的比較..........................................................79 3-4-1-3 結論......................................................................................79 3-4-2 TMA 熱機械分析.......................................................................80 3-4-3 熱重分析儀(TGA)的分析結果……………………………….81 3-4-3-1 相同環氧樹脂不同硬化劑的比較......................................82 3-4-3-2 相同硬化劑不同環氧樹脂的比較......................................82 3-4-3-3 結論......................................................................................83. 第四章 結論............................................................................................84. 第五章 參考文獻………………………………………………………86. x.
(15) 表目錄 頁次 Table.1-1 Merits of Adhesives for Optical Applications………………....5 Table.1-2 The relationships between the refractive index of resins and the edge thickness and mass of spherical lenses……………………………..7 Table.1-3 Comparisons of Optical Materials…………………………...18 Table.1-4 Comparisons of Refractive Indices of Inorganic and Organic Materials………………………………………………………………..19 Table.2-1 Melt mixing temperature and calculation of the amount of CAⅠ for equivalent ratio of epoxy to CAⅠ…………………………...45 Table.2-2 Melt mixing temperature and calculation of the amount of CAⅡfor equivalent ratio of epoxy to CAⅡ……………………………46 Table2-3 Melt mixing temperature and calculation of the amount of CAⅢ for equivalent ratio of epoxy to CAⅢ Table.2-4 Melt mixing temperature and calculation of the amount of CAⅣ for equivalent ratio of epoxy to CAⅣ…………………………...49 Table.3-1 環氧樹脂與 CAⅠ動態 DSC 分析結果……………………61 Table.3-2 環氧樹脂與 CAⅡ動態 DSC 分析結果……………………62 Table.3-3 Curing conditions of epoxy/CAⅠCAⅡ systems…………...63 Table.3-4 環氧樹脂與 CAⅢ動態 DSC 分析結果…………………….64 Table.3-5 環氧樹脂與 CAⅣ動態 DSC 分析結果…………………….64 Table.3-6 Curing conditions of epoxy/ CAⅢCAⅣ systems…………..65. xi.
(16) Table.3-7 Kinetic data of Epoxy systems………………………………67 Table.3-8 交聯產物之凝膠分率結果…………………………………71 Table.3-9 Refractive Index of Epoxy Systems…………………………73 Table.3-10 Results of UV/VIS Transparency of Epoxy Resins Systems.........................................................................................77 Table.3-11 由 DSC 所決定的各系統玻璃轉化溫度………………….78 Table.3-12 交聯產物之 TMA 分析結果………………………………80 Table.3-13 交聯產物之 TGA 分析結果……………………………….81. xii.
(17) 圖目錄 頁次 Figure.1-1 Bisphenol A 環氧樹脂的化學構造與構造單體機能………8 Figure.1-2 三級胺催化下環氧樹脂與酸肝硬化反應機構…………...11 Figure.1-3 三級胺催化下硫醇與環氧樹脂硬化反應機構…………...12 Figure.1-4 Time-Temperature-Transformation （ TTT ） 樹 脂 硬 化 流 變 圖………………………………………………………………………..14 Figure.1-5 DSC 恆溫交聯反應之放熱曲線圖………………………...16 Figure.1-6 Refractive index of Ti-PSF and Ti-PEK systems with different titanium oxide content where it has been assumed that the titanium tetraisopropoxide is converted to TiO2………………………………….23 Figure.3-1 EpoxyⅠ1H-NMR…………………………………………...91 Figure.3-2 EpoxyⅠ13C-NMR…………………………………………..92 Figure.3-3. EpoxyⅠ的紅外線光譜…………………………………….93 Figure.3-4 EpoxyⅠMass 圖譜…………………………………………94 Figure.3-5 EpoxyⅡ1H-NMR…………………………………………...95 Figure.3-6 EpoxyⅡ13C-NMR…………………………………………..96 Figure.3-7 EpoxyⅡ的紅外線光譜……………………………………..97 Figure.3-8 EpoxyⅡMass 圖譜………………………………………….98 Figure.3-9 EpoxyⅢ1H-NMR…………………………………………...99. xiii.
(18) Figure.3-10 EpoxyⅢ13C-NMR………………………………………..100 Figure3-11. EpoxyⅢ的紅外線光譜…………………………………..101 Figure.3-12 EpoxyⅢMass 圖譜……………………………………….102 Figure.3-13 Dynamic DSC of 830LVP/CAⅠ…………………………103 Figure.3-14 Dynamic DSC of EpoxyⅠ/CAⅠ………………………..104 Figure.3-15 Dynamic DSC of EpoxyⅡ/CAⅠ………………………..105 Figure.3-16 Dynamic DSC of EpoxyⅢ/CAⅠ………………………..106 Figure.3-17 Dynamic DSC of EpoxyⅠ/CAⅡ………………………..107 Figure.3-18 Dynamic DSC of EpoxyⅡ/CAⅡ……………………….108 Figure.3-19 Dynamic DSC of EpoxyⅢ/CAⅡ……………………….109 Figure.3-20 Dynamic DSC of EpoxyⅠ/CAⅢ……………………….110 Figure.3-21 Dynamic DSC of EpoxyⅡ/CAⅢ……………………….111 Figure.3-22 Dynamic DSC of EpoxyⅢ/CAⅢ……………………….112 Figure.3-23 Dynamic DSC of EpoxyⅠ/CAⅣ……………………….113 Figure.3-24 Dynamic DSC of EpoxyⅢ/CAⅣ……………………….114 Figure.3-25 EpoxyⅠ/CAⅠ ln(F/Tm2)對 1/Tm做圖……………….115 Figure.3-26 EpoxyⅢ/CAⅠ ln(F/Tm2)對 1/Tm做圖……………….116 xiv.
(19) Figure.3-27 EpoxyⅡ/CAⅡ ln(F/Tm2)對 1/Tm做圖………………117 Figure.3-28 EpoxyⅠ/CAⅣ ln(F/Tm2)對 1/Tm做圖………………118 Figure.3-29 EpoxyⅢ/CAⅣ ln(F/Tm2)對 1/Tm做圖………………119 Figure.3-30 FT-IR spectrum of EpoxyⅠ/CAⅠ……………………..120 Figure.3-31 FT-IR spectrum of EpoxyⅡ/CAⅠ……………………..121 Figure.3-32 FT-IR spectrum of EpoxyⅢ/CAⅠ……………………..122 Figure.3-33 FT-IR spectrum of EpoxyⅠ/CAⅡ……………………..123 Figure.3-34 FT-IR spectrum of EpoxyⅡ/CAⅡ……………………..124 Figure.3-35 FT-IR spectrum of EpoxyⅢ/CAⅡ……………………..125 Figure.3-36 FT-IR spectrum of EpoxyⅠ/CAⅢ……………………..126 Figure.3-37 FT-IR spectrum of EpoxyⅡ/CAⅢ……………………..127 Figure.3-38 FT-IR spectrum of EpoxyⅢ/CAⅢ……………………..128 Figure.3-39 FT-IR spectrum of EpoxyⅠ/CAⅣ……………………..129 Figure.3-40 FT-IR spectrum of EpoxyⅢ/CAⅣ……………………..130 Figure.3-41 UV-VIS spectrum of EpoxyⅠ cured with 4 different curing agent………………………………………………………………….131 Figure.3-42 UV-VIS spectrum of EpoxyⅡ cured with 3 different curing agent………………………………………………………………….132. xv.
(20) Figure.3-43 UV-VIS spectrum of EpoxyⅢ cured with 4 different curing agent………………………………………………………………….133 Figure.3-44 UV-VIS spectrum of CA Ⅰ cured 4 different epoxy resins…………………………………………………………………134 Figure.3-45 UV-VIS spectrum of CA Ⅱ cured 3 different epoxy resins…………………………………………………………………135 Figure.3-46 UV-VIS spectrum of CA Ⅲ cured 3 different epoxy resins…………………………………………………………………136 Figure.3-47 UV-VIS spectrum of CA Ⅳ cured 2 different epoxy resins…………………………………………………………………137 Figure.3-48 DSC results of EpoxyⅠ cured with 4 different curing agent…………………………………………………………………138 Figure.3-49 DSC results of EpoxyⅡ cured with 3 different curing agent…………………………………………………………………139 Figure.3-50 DSC results of EpoxyⅢ cured with 4 different curing agent…………………………………………………………………140 Figure.3-51 DSC results of CAⅠ cured 4 different epoxy resins….141 Figure.3-52 DSC results of CAⅡ cured 3 different epoxy resins….142 Figure.3-53 DSC results of CAⅢ cured 3 different epoxy resins….143 Figure.3-54 DSC results of CAⅣ cured 2 different epoxy resins….144 Figure.3-55 TMA results of 830LVP/CAⅠ system………………...145 Figure.3-56 TMA results of EpoxyⅠ/CAⅠ system………………..146. xvi.
(21) Figure.3-57 TMA results of EpoxyⅡ/CAⅠ system……………….147 Figure.3-58 TMA results of EpoxyⅢ/CAⅠ system……………….148 Figure.3-59 TMA results of EpoxyⅠ/CAⅡ system……………….149 Figure.3-60 TMA results of EpoxyⅡ/CAⅡ system……………….150 Figure.3-61 TMA results of EpoxyⅢ/CAⅡ system……………….151 Figure.3-62 TMA results of EpoxyⅠ/CAⅢ system……………….152 Figure.3-63 TMA results of EpoxyⅡ/CAⅢ system……………….153 Figure.3-64 TMA results of EpoxyⅢ/CAⅢ system……………….154 Figure.3-65 Thermogravimetric analysis of Epoxy Ⅰ cured with 4 different curing agent………………………………………………..155 Figure.3-66 Thermogravimetric analysis of Epoxy Ⅱ cured with 3 different curing agent………………………………………………..156 Figure.3-67 Thermogravimetric analysis of Epoxy Ⅲ cured with 4 different curing agent………………………………………………..157 Figure.3-68 Thermogravimetric analysis of CA Ⅰ cured 4 different epoxy resins…………………………………………………………158 Figure.3-69 Thermogravimetric analysis of CA Ⅱ cured 3 different epoxy resins…………………………………………………………159 Figure.3-70 Thermogravimetric analysis of CA Ⅲ cured 3 different epoxy resins…………………………………………………………160 Figure.3-71 Thermogravimetric analysis of CA Ⅳ cured 2 different epoxy resins…………………………………………………………161 xvii.
(22) Figure.3-72 EpoxyⅠ/CAⅠ FT-IR spectrum 相減疊圖……………162 Figure.3-73 EpoxyⅡ/CAⅠ FT-IR spectrum 相減疊圖……………163 Figure.3-74 EpoxyⅢ/CAⅠ FT-IR spectrum 相減疊圖……………164 Figure.3-75 EpoxyⅠ/CAⅡ FT-IR spectrum 相減疊圖……………165 Figure.3-76 EpoxyⅡ/CAⅡ FT-IR spectrum 相減疊圖……………166 Figure.3-77 EpoxyⅢ/CAⅡ FT-IR spectrum 相減疊圖……………167 Figure.3-78 EpoxyⅠ/CAⅢ FT-IR spectrum 相減疊圖……………168 Figure.3-79 EpoxyⅡ/CAⅢ FT-IR spectrum 相減疊圖……………169 Figure.3-80 EpoxyⅢ/CAⅢ FT-IR spectrum 相減疊圖……………170 Figure.3-81 EpoxyⅠ/CAⅣ FT-IR spectrum 相減疊圖……………171 Figure.3-82 EpoxyⅢ/CAⅣ FT-IR spectrum 相減疊圖……………172. xviii.
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