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研究生:鍾沅甫
研究生(外文):Yuan Fu Jhong
論文名稱:靜態與動態環境對高分子紫外光固化之影響
論文名稱(外文):The Influence of Static and Kinetic Environments on Polymer UV-Curing
指導教授:芮祥鵬芮祥鵬引用關係
口試委員:戴子安程耀毅
口試日期:2012-07-13
學位類別:碩士
校院名稱:國立臺北科技大學
系所名稱:有機高分子研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:中文
論文頁數:96
中文關鍵詞:紫外光固化Photo-DSC流變動力學Real-time FTIR儲存模數流變儀KamalMalkin
外文關鍵詞:UV curingPhoto-DSCrheological kineticReal-time FTIRstorage modulusrheometerKamalMalkin
相關次數:
  • 被引用被引用:1
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本研究為探討三官能基自由基樹脂及環氧系單體陽離子光固化系統於恆溫條件下靜態及動態光固化所產生之差異。自由基光固化系統將具有三個壓克力基之Trimethylolpropane triacrylate (TMPTA)加入裂解型光起始劑HMPP,陽離子光固化系統則是將具有環氧基之3,4-Epoxycyclohexylmethyl-3,4-cyclohexanecarboxylate (CELLOXIDE 2021P)加入路易士酸光起始劑UVI 6976後分別配置不同濃度再曝照紫外光形成網狀交聯結構。
固化過程以Photo-DSC亦稱為DPA (Double Beam Photocalorimetric Accessory)恆溫靜置下偵測反應放熱數值,換算得熱能轉化率,代入Kamal方程式;Real-time FT-IR則以穿透式掃描外加紫外光設備,藉由特徵峰與標準峰比值的變化換算得到其轉化率,亦代入Kamal方程式並輔佐DPA進行靜態光固化的數據比較;而流變儀於光固化過程中,自由基及陽離子樹脂在動態(dynamic)狀態產生黏彈性指標儲存模數(G’)之轉化率,代入Malkin and Kulichikhin方程式,則為動態光固化動力學數據。
自由基及陽離子光固化系統於靜態量測中(DPA、RTIR)皆觀察到在恆溫環境下添加光起始劑濃度存在一臨界值;動態量測(流變儀)發現自由基系統亦有一極限濃度存在並且具有Trommsdorff effect,陽離子系統固化過程G’∞會因鏈成長聚合過程中路易士酸光起始劑之中間產物受到干擾使G’增長受限。


The differences of static and kinetic behaviors under constant temperature while use three functional radicals resin and epoxy cationic type UV curable resins. Three different in situ monitoring techniques including photocalorimetry(DPA)、rheometer
(Physica) and real time FT-IR(RT-IR) were used in order to investigate the kinetics of the photopolymerization process.
The free radical type photopolymerization mixtures of trimethylolpropane triacrylate (TMPTA) which has three acrylic groups was added with cleavage photoinitiator HMPP, and the cationic type photopolymerization mixtures of 3,4-Epoxycyclohexylmethyl-3,4-cyclohexanecarboxylate(CELLOXIDE 2021P) that was added with Lewis acid photoinitiator UVI 6976. After that, we prepare different concentrations respectively then formed cross-linking network structures by irradiated ultraviolet beam.
During the curing process, Photo-DSC which is also called DPA (Double Beam Photocalorimetric Accessory) was used to detect the endothermic or exothermic reaction heats, then converting to calorimetric conversions and were used for Kamal’s model;Real-time FTIR was used to investigate the evolution about the ratio of characteristics peak to standard peak by adding ultraviolet beam, then converting to conversions and were also used for Kamal’s model to test and verify the UV-curing’s data under static behavior with DPA. On the other hand, rheometer was used to get rheological conversions that were calculated from storage modulus (G’) during curing processes, the values are used for Malkin and Kulichikhin’s model to indicate the data about kinetic behavior UV-curing.
Free radical and cationic UV curable systems in the static measurement(DPA、RTIR) were both observed to have critical values for the amounts of photoinitiator in isothermal environment;In the kinetic measurement (Physica), we found that Free radical type also have an extreme values and existed ”Trommsdorff effect”. However, the G’∞ of cationic photopolymerization was affected due to chain growth mechanism interfered with dynamic shear strain on intermediate of decomposed photoinitiator.

摘 要 I
ABSTRACT II
誌謝 IV
表目錄 XIV
第一章 緒論 1
1.1. 前言 1
1.2. 研究動機 3
第二章 文獻回顧 4
2.1 紫外光的定義與應用 4
2.1.1 紫外光的定義 4
2.1.2 紫外光的分類 5
2.2 紫外光固化樹脂 6
2.3 光固化樹脂的起源 7
2.4 光固化樹脂的種類 9
2.4.1 乙烯基類反應性樹脂(自由基光固化體系) 10
2.4.2 非乙烯基類反應性樹脂(陽離子光固化體系) 11
2.4.3 丙烯酸酯系與環氧樹脂系樹脂的比較 15
2.5 光固化樹脂的組成 17
2.5.1 寡聚物(oligomer) 18
2.5.2 光起始劑(photoinitiator) 21
2.5.3 單體(Monomer) 23
2.5.4添加劑(Additives) 25
2.5.5助劑(Auxiliaries) 26
2.5.6光敏劑(Photosensitizer) 26
2.6 影響紫外光固化之因素 27
2.6.1 紫外光燈的波長、強度 27
2.6.2 樣品厚度 28
2.6.3 溫度影響 29
2.7 光固化動力學 30
2.7.1自催化方程式 30
2.7.2 DSC自催化動力學 32
2.7.3 流變自催化動力學 33
第三章 實驗部分 35
3.1 實驗藥品 35
3.1.1 壓克力系自由基光固化系統 35
3.1.1.1 反應單體 35
3.1.1.2 光起始劑 35
3.1.2 環氧樹脂系陽離子光固化系統 36
3.1.2.1 反應單體 36
3.1.2.2 光起始劑 36
3.2 實驗儀器 37
3.2.1示差微分雙光卡量計 (DPA) 37
3.2.2 Physica動態流變儀 39
3.2.2.1雙平板(parallel plate) 39
3.2.2.2紫外光固化式流變裝置 40
3.2.3 傅立葉轉換紅外線光譜儀(FT-IR) 41
3.3 實驗流程 42
3.4 實驗方法 42
3.4.1 樣品製備 42
3.4.2 動力學分析 43
3.4.2.1 Photo量熱法(Photocalorimetric method) 43
3.4.2.2 UV固化流變法(UV curing rheological method) 43
3.4.2.3 RTIR量測法(Real tine FT-IR measure method) 44
3.5 不同測量法對光固化樹脂之動力學比較 44
3.5.1 DPA數據之動力學分析 44
3.5.2 流變儀數據之動力學分析 45
3.5.3 RTIR數據之動力學分析 47
第四章 結果與討論 49
4.1 自由基光固化系統動力學分析 49
4.1.1 DPA動力學分析 49
4.1.2 流變動力學分析 52
4.1.3 RTIR動力學分析 56
4.1.4 動力學綜合比較 60
4.1.4.1 光固化反應Normalized轉化率比較 60
4.1.4.2 轉化速率-轉化率綜合比較 64
4.2 陽離子光固化系統動力學分析 69
4.2.1 DPA動力學分析 70
4.2.2 流變動力學分析 73
4.2.3 RTIR動力學分析 77
4.2.4 靜態與動態光固化動力學綜合比較 80
4.2.3.1 光固化反應理論轉化率比較 80
4.2.3.2 動力學轉化速率-轉化率比較 84
第五章 結論 90
第六章 參考文獻 92


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