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研究生:葉柔含
研究生(外文):Rou-HanYeh
論文名稱:分子作用力對團聯共聚物混摻物有序-無序轉換與結晶行為的影響
論文名稱(外文):The Effect of Molecular Interactions on the Order-Disorder Transition and Crystallization Behavior of Block Copolymer Blends
指導教授:羅介聰
指導教授(外文):Chieh-Tsung Lo
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學工程學系
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:2016
畢業學年度:104
語文別:中文
論文頁數:125
中文關鍵詞:團聯共聚物相行為非等溫結晶有序-無序轉換氫鍵混摻
外文關鍵詞:block copolymerphase behaviornonisothermal crystallizationhydrogen bondingorder-disorder transitionblends
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本研究以團聯共聚物polystyrene-block-poly(ethylene oxide) (PS-b-PEO)與sodium dodecyl sulfate (SDS)以及均聚物poly(acrylic acid) (h-PAA)進行混摻,觀察其相行為及結晶行為。
對稱型PS-b-PEO與SDS混摻時,PEO與SDS形成complex但不影響PS-b-PEO之層狀結構。添加30 wt% SDS時,較多SDS進入PEO domain中,使其domain size變大,此外,SDS與PEO形成complex會破壞PEO之對稱結構,使PEO不易結晶,因此PS-b-PEO之半結晶時間增加、結晶度與結晶溫度則下降,結晶速率也明顯變慢。此外,SDS與PEO鏈段相容,與PS鏈段則不相容,SDS與PS鏈段之間的排斥力會干擾PS-b-PEO之層狀結構,使PS-b-PEO有序-無序轉換溫度下降,較易成為無序結構。
將PS-b-PEO與不同分子量之h-PAA進行摻合,由於PEO與PAA可以形成氫鍵,因此h-PAA進入PEO domain中,使其domain尺寸變大,但不改變層狀結構。當摻入10 wt% 分子量較小的h-PAA時,其結晶溫度、結晶層厚度、結晶度、結晶速率與晶粒大小均減小。混摻20 wt%的h-PAA時,與PEO鏈段形成氫鍵的PAA阻礙了PEO的結晶,造成混摻分子量較小的h-PAA時,產生冷結晶現象,混摻分子量較大的h-PAA時PEO無結晶產生。

We studied the nonisothermal crystallization and order-disorder transition of polystyrene-block-poly(ethylene oxide) (PS-b-PEO)/sodium dodecyl sulfate (SDS) blends and PS-b-PEO/poly(acrylic acid) (h-PAA) blends.
The PS-b-PEO/SDS blends exhibited a lamellae structure. Because the PEO block and SDS were miscible, whereas the PS block and SDS were immiscible, SDS molecules were segregated into the PEO microdomains. The PEO and SDS complex disturbed the symmetry structure of PEO, thereby prohibiting the PEO crystallization. This resulted in the decrease of crystallization temperature, onset crystallization temperature, and degree of crystallinity. When 30 wt% SDS was added in PEO, the half crystallization time was prolonged considerably. The formation of PEO/SDS complex also decreased the order-disorder transition temperature because of the repulsion between SDS and PS chains.
In PS-b-PEO/h-PAA blends, the addition of h-PAA in PS-b-PEO decreased the crystal thickness, grain size, crystallization temperature, onset crystallization temperature, and degree of crystallinity. This was attributed to the formation of hydrogen bonding between PEO and PAA that disturbed the PEO crystallization. Furthermore, h-PAA was localized in the PEO domains, which increased the domain size without changing the microstructure of PS-b-PEO. Such effects were more pronounced when small molecular weight of h-PAA was blended. Cold crystallization occurred when 20 wt% small molecular weight h-PAA was added in PS-b-PEO, whereas that with a high molecular weight of h-PAA, the hydrogen bonding between PEO and PAA prevented PEO from crystallization, and PEO crystallization did not occur.

摘要 II
Extend abstract III
誌謝 XVIII
總目錄 XIX
表目錄 XXI
圖目錄 XXII
第一章 緒論 1
1.1前言 1
1.2研究動機 2
第二章 文獻回顧 3
2.1共聚物(Copolymer) 3
2.2自組裝(self-assembly) 4
2.3高分子混摻之微相分離 6
2.3.1團聯共聚物之微相分離 6
2.3.2有序-無序轉換(order-disorder transition) 10
2.3.3團聯共聚物與均聚物混摻之微相分離 15
2.3.4結晶性高分子之微相分離 18
2.4高分子混摻系統之作用力 19
2.4.1高分子混摻之氫鍵作用力 19
2.4.2高分子混摻系統之離子 – 偶極作用力 23
2.5高分子之結晶行為 27
2.5.1高分子之結晶形態 27
2.5.2 結晶動力學 27
2.5.3等溫結晶動力學 28
2.5.4非等溫結晶動力學 30
第三章 實驗 32
3.1 藥品 32
3.2分析儀器 34
3.3實驗步驟 35
3.3.1 PS/SDS、h-PEO/SDS與PS-b-PEO/SDS混摻物樣品製備 35
3.3.2 PS/h-PAA、h-PEO/h-PAA與PS-b-PEO/h-PAA混摻物樣品製備 …………………………………………………………………...36
3.4實驗流程圖 37
第四章 結果與討論 38
4.1團聯共聚物/界面活性劑之混摻物 38
4.1.1 h-PEO(Mn = 12000 g/mol)/SDS混摻物之作用力 39
4.1.2 PS-b-PEO(Mn = 10000-b-11500 g/mol)/SDS混摻物之作用力 41
4.1.3 h-PEO(Mn = 12000 g/mol)/SDS混摻物之相行為 45
4.1.4 PS-b-PEO(Mn = 10000-b-11500 g/mol)/SDS混摻物之相行為 56
4.1.5 h-PEO/SDS(Mn = 12000 g/mol)混摻物之非等溫結晶動力學 75
4.1.6 PS-b-PEO (Mn = 10000-b-11500 g/mol)/SDS混摻物之非等溫結晶動力學 79
4.2團聯共聚物/均聚物之混摻 83
4.2.1 PS-b-PEO/h-PAA混摻物之相容性 83
4.2.2 PS-b-PEO/h-PAA混摻物之氫鍵強度 86
4.2.3 PS-b-PEO/h-PAA混摻物之非等溫結晶行為 92
4.2.4 PS-b-PEO/h-PAA混摻物之之非等溫結晶動力學 107
第五章 結論 115
第六章 參考資料 117

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