臺灣博碩士論文加值系統

本文之目的，乃探討三種特用添加劑，分別為：(1) 反應性微膠顆粒(2)奈米級與次微米級核殼型橡膠(core-shell rubber)添加劑及(3)矽烷改質蒙特納石黏土(montmorillonite clay，MMT)，其對苯乙烯/不飽和樹脂/特用添加劑三成份系統之聚合固化動力及玻璃轉移溫度影響。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，吾人亦以動態機械測定儀(DMA)測量之。

The effects of reactive microgel (RM) and nano-scale and sub-micron scale core shell rubbers (CSR) as low-profile additives (LPA), and silane treated montmorillonite clay (MMT) on the cure kinetics and glass transition temperatures for styrene/unsaturated polyester/additive ternary systems have been investigated. 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 dynamic mechanical analysis (DMA).

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 乙烯基酯樹脂---------------------------------------------------------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核殼型橡膠增韌劑之效應------------------------------------------19
2-6不飽和聚酯樹脂系統之玻璃轉移溫度之研究------------------22
2-7蒙特納石黏土-高分子奈米複合材料研究--------------------------25
第三章 實驗方法---------------------------------------------------------------28
3-1 原料-----------------------------------------------------------------------28
3-1-1不飽和聚酯樹脂-----------------------------------------------28
3-1-2奈米級與次微米級核殼型橡膠之特用添加劑-----------30
3-1-3反應性微膠顆粒-----------------------------------------------32
3-1-4蒙特納石黏土之合成原料-----------------------------------34
3-2 實驗儀器---------------------------------------------------------------35
3-3 實驗步驟---------------------------------------------------------------36
3-3-1 PK-805型clay之鈉活性化處理------------------------------36
3-3-2 Silane-treated MMT 之製備--------------------------------36
3-3-3 DSC反應動力測試步驟---------------------------------------37
3-3-4 DMA三成份試片製備-----------------------------------------38
3-3-5 ST/UP/additive三成份系之相容性---------------------------41
3-4性質測試與分析------------------------------------------------------42
3-4-1熱分析-------------------------------------------------------------42
3-4-2 FTIR定量分析--------------------------------------------------44
3-4-3 DMA理論基礎--------------------------------------------------55
第四章 結果與討論------------------------------------------------------------56
4-1 Silane-Treated MMT FTIR定量分析-----------------------------56
4-2 微觀結構--------------------------------------------------------------76
4-2-1 ST/UP兩成份系之微觀結構---------------------------------76
4-2-2 St/VER/奈米級與次微米級核殼型橡膠系統(E0系統)--80
4-2-3 ST/VER/奈米級與次微米級核殼型橡膠系統(E1系統)-93
4-2-4 St/UP/奈米級與次微米級核殼型橡膠系統SEM微觀型態結構之整體比較-------------------------------107
4-2-5 St/VER/蒙特鈉石黏土(MMT)三成份系統----------------115
4-3 DSC反應動力-------------------------------------------------------120
4-3-1 不同苯乙烯對VER之C=C雙鍵莫耳比(MR)之純VER樹脂DSC反應動力-------------------------------------------------120
4-3-2 ST/UP 雙成份系之DSC反應動力-------------------------124
4-3-3 ST/UP/RM三成份系之DSC反應動力--------------------128
4-3-3-1 ST/VER/10% RM三成份系之DSC反應動力--------128
4-3-3-2 ST/MA-PG/10% RM三成份系之DSC反應動力----133
4-3-3-3 ST/MA-PA-PG/10% RM三成份系之DSC反應動--138
4-3-4 ST/UP/CSR三成份系之DSC反應動力-------------------143
4-3-4-1 ST/VER/CSR(E0-30)三成份系之DSC反應動力----143
4-3-4-2 ST/VER/CSR(E0-60)三成份系之DSC反應動力----148
4-3-4-3 ST/VER/CSR(E0-260)三成份系之DSC反應動力--152
4-3-4-4 ST/VER/CSR(E1-30)三成份系之DSC反應動力----156
4-3-4-5 ST/VER/CSR(E1-60)三成份系之DSC反應動力----160
4-3-4-6 ST/VER/CSR(E1-30)三成份系之DSC反應動力----164
4-3-4-7 ST/ VER / 5% CSR 之三成份系之DSC反應動力--168
4-3-4-8 ST/MA-PG/ 5% CSR三成份系之DSC反應動力----173
4-3-4-9 ST/MA-PA-PG/ 5% CSR三成份系之DSC反應動力---------------------------------------------------------------182
4-3-5 ST/VER/Silane-Treated MMT三成份系統-------------------183
4-3-5-1 ST/VER/Silane-Treated MMT三成份系統------------183
4-3-5-2 ST/UP/5% Silane-Treated MMT三成份系之DSC反應動力------------------------------------------------------------188
4-4 FT-IR反應動力-----------------------------------------------------------192
4-4-1 校正曲線------------------------------------------------------192
4-4-2純粹乙烯基酯樹脂(Vinyl ester resin , VER)系統反應動
力-----------------------------------------------------------------198
4-4-3 由FT-IR計算不飽和聚酯C=C雙鍵轉化率------------201
4-4-3-1純粹乙烯基酯樹脂(Vinyl ester resin , VER)系統反應動力------------------------------------------------------201
4-4-3-2純粹MA-PG系統反應動力---------------------------205
4-4-3-3純粹MA-PA-PG系統反應動力----------------------209
4-4-3-4 ST/UP 雙成份系統比較------------------------------213
4-4-3-5 ST/VER/CSR三成份系統--------------------------------215
4-4-3-5-1 ST/VER/5% CSR(E0-30)三成份系統------------215
4-4-3-5-2 ST/VER/5% CSR(E0-60)三成份系統------------219
4-4-3-5-3 ST/VER/5% CSR(E0-260)三成份系統-----------223
4-4-3-5-4 ST/VER/5% CSR(E1-30)三成份系統------------227
4-4-3-5-5 ST/VER/10% CSR(E1-30)三成份系統-----------231
4-4-3-5-6 ST/VER/5% CSR(E1-260)三成份系統-----------235
4-4-3-5-7 ST/VER/CSR三成份系統之比較-----------------239
4-5 Takayanagi 機械模式與各相區之玻璃轉移溫度-------------------247
4-5-1以DMA測定ST/VER/CSR三成份係聚合固化樣品之Tg--------------------------------------------------------------249
4-5-1-1純粹乙烯基酯樹脂(Vinyl ester resin , VER)系統------------------------------------------------------------249
4-5-1-2 ST/UP雙成份系統之比較---------------------------255
4-5-2添加反應性微膠顆粒RM之ST/ UP/ RM聚合固化樣品之三成份系之DMA測試-------------259
4-5-2-1 ST/ VER / 10% RM 之三成份系-----------------259
4-5-2-2 ST/ MA-PG/ 10% RM 之三成份系--------------263
4-5-2-3 ST/ MA-PA-PG/ 10% RM 之三成份系---------268
4-5-3 ST/ VER / CSR 之三成份系----------------------------274
4-5-3-1 ST/ VER / CSR(E0-30) 之三成份系-------------274
4-5-3-2 ST/ VER/ CSR(E0-60) 之三成份系--------------279
4-5-3-3 ST/ VER / CSR(E0-260) 之三成份系-----------283
4-5-3-4 ST/ VER / CSR(E1-30) 之三成份系-------------287
4-5-3-5 ST/ VER / CSR(E1-60) 之三成份系-------------292
4-5-3-6 ST/ VER / CSR(E1-260) 之三成份系-----------297
4-5-3-7 ST/ UP / 5% CSR 之三成份系--------------------301
4-5-4 ST/ VER / Silane-Treated MMT 之三成份系--------310
4-5-5 ST/ UP / 5% Silane-Treated MMT 之三成份系-----314
第五章 結論-----------------------------------------------------------------318
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