臺灣博碩士論文加值系統

本文乃探討添加反應性微膠顆粒型抗收縮劑（LPA）、奈米級核殼型橡膠（CSR）及蒙特納石黏土（MMT），對其ST/UP/Additive三成份系之聚合固化動力及玻璃轉移溫度影響。吾人利用小角度X-ray散射儀(SAXS)測定不飽和聚酯(UP)之稀薄苯乙烯(ST)溶液之散射強度，再利用Guinier Law計算UP之環動半徑(Radius of Gyration)，以瞭解UP分子擴散至蒙特納石黏土層間之難易程度。吾人利用微分掃描熱分析儀(DSC)及傅立葉轉換紅外光譜儀(FTIR)測量ST/UP/additive三成份系在聚合固化過程中之反應動力。最後依據Takayanagi機械模式，ST/UP/additive三成份系聚合固化後的樣品，其在各相區之玻璃轉移溫度，吾人亦以熱刺激去極化電流分析儀(TSC)及動態機械測定儀(DMA)測量之。

The effects of reactive microgel (RM) particle type of low-profile additives (LPA), nano-scale core-shell rubber (CSR) tougheners, and montmorillonite clay (MMT) on the cure kinetics and glass transition temperatures for styrene/unsaturated polyester/additive ternary systems have been investigated. The scattering intensity of unsaturated polyester (UP) in dilute styrene solution was measured by the method of small angle X-ray scattering (SAXS), and the radius of gyration of the UP molecule can then be calculated by using the Guinier law. Hence, the ease at which the UP molecule can diffuse into the gallery spacing of the MMT clay can be evaluated. The reaction kinetics for the ST/UP/additive ternary system during the cure was measured by differential scanning calorimetry (DSC)and Fourier transform infrared spectrometry (FTIR). Finally, based on the Takayanagi mechanical models, the glass transition temperature in each region of the cured samples for ST/UP/additive ternary systems has been measured by the method of thermally stimulated currents (TSC) and the method of dynamic mechanical analysis (DMA).

目錄
中文摘要-------------------------------------------------------------------------I
英文摘要-------------------------------------------------------------------------II
誌謝-------------------------------------------------------------------------------III
圖表索引------------------------------------------------------------------------VI
第一章 緒論-----------------------------------------------------------------------1
1-1 高分子複合材---------------------------------------------------------1
1-2 抗收縮劑---------------------------------------------------------------3
1-3 反應性微膠顆粒------------------------------------------------------4
1-4 核殼型(Core-Shell Rubber, CSR)改質不飽和聚酯樹脂--------5
1-5 蒙特納石黏土(Montmorillonite, MMT)及其高分子奈米複合材料---------------------------------------------------------------------6
1-6 研究範疇---------------------------------------------------------------7
第二章 文獻回顧-----------------------------------------------------------------8
2-1不飽和聚酯與苯乙烯之交聯共聚合反應--------------------------8
2-2不飽和聚酯樹脂之反應動力學模式之研究---------------------11
2-3不飽和聚酯樹脂之聚合固化研究---------------------------------16
2-4低收縮不飽和聚酯樹脂之聚合固化研究------------------------17
2-5反應性微膠顆粒型抗收縮劑之效應------------------------------19
2-6核殼型橡膠增韌劑之效應------------------------------------------20
2-7不飽和聚酯樹脂系統之玻璃轉移溫度之研究---------------------23
2-8蒙特納石黏土-高分子奈米複合材料研究--------------------------26
2-9高分子稀薄溶液之環動半徑研究------------------------------------27
第三章 實驗方法---------------------------------------------------------------31
3-1 原料-----------------------------------------------------------------------31
3-2 實驗儀器---------------------------------------------------------------37
3-3 實驗步驟---------------------------------------------------------------38
3-3-1 DSC溶液製備步驟---------------------------------------------38
3-3-2 DSC反應動力測試步驟---------------------------------------40
3-3-3 DMA與TSC三成份試片製備--------------------------------42
3-3-4熱刺激去極化電流（Thermally Stimulated Current, TSC）實驗測試--------------------------------------------------------45
3-3-5 動態機械分析(Dynamic Mechanical Analyzer，DMA)---50
3-3-6 ST/U/additive三成份系之相容性----------------------------50
3-3-7利用SAXS測定不飽和聚酯之環動半徑--------------------51
3-4性質測試與分析------------------------------------------------------52
3-4-1熱分析-------------------------------------------------------------46
3-4-2 FTIR定量分析--------------------------------------------------54
3-4-3 TSC的理論基礎------------------------------------------------63
3-4-3-1 熱刺激去極化分析儀 (TSC) 的物理原理-----------63
3-4-4 DMA理論基礎-------------------------------------------------68
3-4-5小角度X-ray散射(SAXS)之相關理論--------------------69
3-4-5-1 X-ray簡介---------------------------------------------------69
3-4-5-2 X光的產生--------------------------------------------------69
3-4-5-3 X光與中子散射--------------------------------------------71
3-4-6 SAXS測定高分子稀薄溶液以求算高分子環動半徑之理論------------------------------------------------------------72
3-4-6-1 Guinier Law-------------------------------------------------72
3-4-6-2 Zimm、Flory和Bueche光散射法------------------------74
3-4-6-3 Zimm Plot---------------------------------------------------76
3-4-7 聚苯乙烯標準樣品在環己烷溶劑中的環動半徑--------77
第四章 結果與討論------------------------------------------------------------78
4-1 ST/UP/additive未反應三成份系之相容性-----------------------78
4-1-1 ST/UP/RM系-------------------------------------------------------78
4-2 微觀結構--------------------------------------------------------------80
4-2-1 ST/UP兩成份系之微觀結構---------------------------------80
4-2-2 ST/UP(MA-PG)/CSR三成份系之微觀結構---------------85
4-2-3 ST/UP/RM三成份系之微觀結構----------------------------88
4-3 DSC反應動力---------------------------------------------------------94
4-3-1 ST/UP(MA-PG)/DV treated MMT三成份系之DSC反應動力-------------------------------------------------------------------94
4-3-2 ST/UP/CSR(Core-shell rubber)三成份系之DSC反應動力 ----------------------------------------------------------------------99
4-3-2-1 ST/UP(MA-PA-PG)/E1-S三成份系之DSC反應動力----------------------------------------------------------------------99
4-3-2-2 ST/UP(MA-PA-PG)/E1-M三成份系之DSC反應動力---------------------------------------------------------------------103
4-3-2-3 ST/UP(MA-PA-PG)/E1-L三成份系之DSC反應動力---------------------------------------------------------------------107
4-3-3 ST/UP/RM(Reactive Microgel)三成份系之DSC反應動力------------------------------------------------------------------111
4-4 Takayanagi 機械模式與各相區之玻璃轉移溫度-------------116
4-4-1 動態機械測試(DMA)---------------------------------------118
4-4-1-1 純粹不飽和聚酯樹脂系統-----------------------------118
4-4-1-2 ST/UP(MA-PA-PG)/CSR之三成份系----------------136
4-4-1-3 ST/UP/RM之三成份系----------------------------------150
4-4-2熱刺激去極化電流測試(TSC)------------------------------160
4-4-2-1純粹不飽和聚酯樹脂系統------------------------------160
4-4-2-2 ST/UP/CSR之三成份系---------------------------------177
4-4-2-3 ST/UP/RM之三成份系----------------------------------197
4-5 小角度X光散射法測定高分子之環動半徑(Rg)--------------210
4-5-1聚苯乙烯標準樣品的環動半徑之測量--------------------210
4-5-2不飽和聚酯在苯乙烯溶劑中的環動半徑-----------------216
第五章 結論--------------------------------------------------------------------222
參考文獻------------------------------------------------------------------------227

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