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研究生:劉玲詩
研究生(外文):Ling-Shih Liou
論文名稱:苯乙烯磺酸鈉-苯乙烯團塊共聚物與十二烷基硫酸鈉混合乳化劑對乳化聚合的效應
論文名稱(外文):Entry in emulsion polymerization using a mixture of sodium polystyrene sulfonate-b-polystyrene and sodium dodecyl sulfate as the surfactant
指導教授:朱侯憲
指導教授(外文):Hou-Hsein Chu
學位類別:碩士
校院名稱:逢甲大學
系所名稱:化學工程學所
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:2009
畢業學年度:97
語文別:中文
論文頁數:98
中文關鍵詞:穩定自由基聚合乳化劑乳化聚合團塊共聚物十二烷基硫酸鈉聚苯乙烯聚苯乙烯磺酸鈉
外文關鍵詞:surfactantentrycaptureblock copolymerstable free-radical polymerizationemulsion polymerizationsodium polystyrene sulfonatepolysytrenesodium dodecyl sulfate
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本實驗主要是觀察以兩親性高分子苯乙烯磺酸鈉-苯乙烯
(Sodium polystyrene sulfonate -b- Polystyrene, NaPSS -b- PS)團塊共聚物之乳化劑對聚苯乙烯乳化聚合中,自由基進入乳液粒子的影響。使用活性自由基聚合製備 NaPSS均聚物的巨起始劑,再與單體苯乙烯進一步聚合成 NaPSS-b-PS的雙團塊共聚物,藉由兩端親水基(NaPSS)與疏水基(PS)的界面性質使具有乳化劑的功能。
合成NaPSS-b-PS的雙團塊共聚物是第一階段以TEMPO為活性自
由基進行聚合 NaSS,使合成具有穩定自由基的巨起始劑
(macroinitiator)NaPSS;再與親油性的單體苯乙烯聚合,形成兩端含有親水基與疏水基之界面性質的 NaPSS-b-PS團塊共聚物(block copolymers),再經由GPC測定出NaPSS團塊Mw為66700,PS團塊的Mw為29300。
在乳化聚合中,觀察乳液的性質與自由基entry 的情形。每個粒
子平均聚合體數目(np)與體積平均粒徑(Dv)是正比的關係,發現單一乳化劑SDS(D 系列)的Dv 值會小於混合乳化劑 NaPSS-b-PS / SDS(E 系列)。E 系列有較低的capture rate (因為PS 有較高的分子量)與較高的聚合速率。
利用吸附層厚度來比較乳化劑在乳液粒子上對於entry 的相關性,發現混合乳化劑比單一乳化劑其吸附層厚度來得小,但是更為穩
定。
將結果與先前的報告加以討論, 比較E 系列與乳化劑使用NaPSS
(Mw=70000)/SDS 的實驗來看,E 系列的粒徑尺寸較小、較低的capture rate 與較快的聚合反應。
This study has prepared sodium polystyrene sulfonate – b –polystyrene (NaPSS-b-PS), which exhibits surface activity with NaPSS block as the hydrophilic moiety and PS block as the hydrophobic moiety. Using mixtures of NaPSS-b-PS and sodium dodecyl sulfate (SDS) as the emulsifier, we performed the emulsion polymerization of styrene and
investigate the entry of oligomeric radicals into the emulsion particles.
The surfactant NaPSS-b-PS was prepared by using the stable free-radical polymerization technique. Using benzoyl peroxide and 2, 2, 6, 6- tetramethyl- piperidinooxy (Tempo) as initiator , we prepared NaPSS macroradical first, then polymerized with styrene to have the PS block.
The NaPSS block has Mw of 66700, and the PS block has Mw of 29300, according to the gel permeation chromatographic determination.
The value of polymer number per particle (np)increases
monotonously with increasing the volume – average particle diameter (Dv). The Dv at turning point of the recipe series of using singlesurfactant of SDS (D series) is smaller than that of the recipe series of using mixed-surfactant of SDS and NaPSS-b-PS (E series).
The E series have the lower capture rate (hence, the PS has higher molecular weight), and the higher polymerization rate.
Compared the results using NaPSS (Mw=70000) and SDS reported elsewhere, we found our E series have the smaller particle size, lower capture rate , and the faster polymerization.
目錄
致謝……………………………………………………………………..Ⅰ
摘要……………………………………………………………………..Ⅲ
英文摘要………………………………………………………………..Ⅴ
縮寫對照表…………………………………………………………… Ⅶ
目錄……………………………………………………………………..Ⅷ
圖目錄…………………………………………………………………..XI
表目錄…………………………………………………………………XVI
第一章 簡介……………………………………………………………1
第二章 實驗……………………………………………………………8
2-1 實驗藥品及預處理………………………………………………..8
2-2 以穩定自由基合成聚苯乙烯磺酸鈉Poly(sodium
styrenesulfonate, NaPSS)……………………………………………9
2-3 合成PS-b-NaPSS(Polystyrene-block- poly(sodium
styrenesulfonate))雙團塊共聚物………………………………….12
2-4 乳化聚合實驗(苯乙烯乳液製備)………………………………13
2-5 乳液分子量測定………………………………………..…………15
2-6 雷射粒子粒徑測定儀 (Laser Particle Analyzing System)粒徑分析……………………………………………………………….….15
2-7 掃描式電子顯微鏡 (Scanning Electron Microscope ) 觀察乳液粒
子…………………………………………………………………..16
2-8 使用Brookfield黏度計測定黏度之方法………………………16
2-9 極限黏度測定………………..……………………………………17
2-10 表面張力測定……………..………………………..……………17
2-11 計算公式…………………………………………..……………..17
第三章 結果與討論……………………………………………………25
3-1 聚苯乙烯磺酸鈉(NaPSS)的合成與鑑定………………………25
3-2 PS-b-NaPSS 的合成、純化與鑑定………………………….……28
3-3 苯乙烯乳化聚合的乳液性質與分析……………………..………31
第四章 結論……………………………………………………………59
參考文獻……………………………………………………………..…61
附錄A 原理………………………….……………………………..…64
A-1 乳化聚合基本理論 ………………………………………..…..…64
A-2 粒子成核理論 ……………………………………..…………..…64
A-3 乳化聚合反應三階段理論修正……………...………………...…67
A-4 乳化劑在粒子表面上的性質……………………………………..68
附錄B 實驗數據結果……………………….……………………...…70
B-1 合成苯乙烯磺酸鈉-苯乙烯團塊共聚物……………….……...…70
B-2 乳化聚合實驗…….…………………………………..…………...70
B-3 掃描式電子顯微鏡之觀察…………………………..………...…76
B-4 比黏度實驗…………………………..…………………………..77
B-5 極限黏度實驗…………………………..………………….……..78
B-6 臨界微胞實驗…………………………..………………….……..80
B-7 乳液粒徑分析…………………………..………………….……..81
附錄C 參考文獻……………………….…………………………..…94
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