含RAFT試劑之馬來醯亞胺/巴比妥酸聚合反應之研究｜國立臺灣科技大學博碩士論文系統

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研究生：	黃景嫻 Jing-Sian Huang
論文名稱：	含RAFT試劑之馬來醯亞胺/巴比妥酸聚合反應之研究 Study for Polymerization of N,N-Bismaleimide-4,4-Diphenylmethane/Barbituric Acid in the Presence of RAFT Agent
指導教授：	陳崇賢 Chorng-Shyan Chern
口試委員:	王復民 Fu-Ming Wang 許榮木 Jung-Mu Hau
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2015
畢業學年度：	103
語文別：	中文
論文頁數：	77
中文關鍵詞：	可逆加成斷鏈鏈轉移聚合法、雙馬來醯亞胺、巴比妥酸、雙苯甲基三硫碳酸酯
外文關鍵詞：	DBTTC, RAFT, BMI, BTA
相關次數：	點閱：269 下載：4
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本實驗主要研究固定莫爾比下(固含量10%)，使用雙馬來醯亞胺(N,N-bismaleimide-4,4-diphenylmethane, BMI)、巴比妥酸(Barbituric acid, BTA)以及雙苯甲基三硫碳酸酯(Dibenzyltrithiocarbonate, DBTTC)，使用可逆加成斷鏈鏈轉移聚合法(RAFT)合成高分子，系統中之固定莫爾比為BMI/BTA ((2/1(mol/mol))，透過聚合反應進行反應動力學。
主要使用微分式掃描熱量分析儀(DSC)，在溫度373-403K反應恆溫一小時，將反應放熱數據利用Excell處理以及利用Matlab數學軟體模擬出m跟n值，再透過Arrhenius方程式計算出活化能(Ea)及頻率因子(A)值，探討不同含量的雙苯甲基三硫碳酸酯(DBTTC)在不同溫度下對反應動力學之影響。

This work was studied on the kinetics of polymerization of N,N-bismaleimide-4,4-diphenylmethane/Barbituric acid in fixed molar ratio with Dibenzyltrithiocarbonate which used as reversible addition-fragmentation chain transfer (RAFT) agent. The system of BMI/BTA = 2/1(mol/mol) was chosen in this work.
The differential scanning calorimerter (DSC) was used to measure the heat of reation for one hour at the isothermal temperature in the range of 373-403 K. The exothermic data of the reaction were calculated via Excell process and used the Matlab mathematical software to simulate the value of m with n, and then through the Arrhenius equation calculated the activation energy (Ea) and frequency factor (A). Therefore, those data could investigate the effect of kinetics of polymerization on different contents of Dibenzyltrithiocarbonate (DBTTC) in different temperature.

目錄
摘要………………………………………………………………………………………………………I
Abstract…………………………………………………………………………………………II
致謝…………………………………………………………………………………………………III
目錄…………………………………………………………………………………………………IV
表目錄……………………………………………………………………………………………VII
圖目錄……………………………………………………………………………………………VIII
第一章	緒論…………………………………………………………………………………1
1 鏈轉移反應…………………………………………………………………………………1
2 可逆加成-斷裂鏈轉移聚合法(RAFT)……………………………………1
3 馬來醯亞胺高分子( Bismaleimides based polymers )……2
4 巴比妥酸( Barbituric acid )…………………………………………………………2
5 研究動機………………………………………………………………………………………………………4
第二章	文獻回顧……………………………………………………………………………………………5
1 自身終止高分歧寡聚物（self terminated oligomers with hyper branched architecture, STOBA)……………………………5
2 活性自由基聚合反應………………………………………………………………6
2.1 引發轉移終止劑活性自由基聚合(Iniferter)…………7
2.2 穩定自由基方式控制聚合反應 (stable free radical polymerization, SFRP)……………………………8
2.3 原子轉移自由基聚合法（atom transfer radical polymerization, ATRP)……………………………………9
2.4 可逆型加成分裂鏈轉移聚合法（reversible addition-fragmentation chain transfer, RAFT)………………………………………………………………………………………………………………………11
3 三嵌段含氟高分子………………………………………………………………………16
4 三硫代碳酸酯…………………………………………………………………………………19
5 RAFT試劑缺陷…………………………………………………………………………………20
6 RAFT聚合應用………………………………………………………………………………………21
第三章	實驗藥品、儀器與步驟……………………………………………………………………22
1 實驗藥品…………………………………………………………………………………………………22
2實驗儀器與設備………………………………………………………………………………………25
3實驗流程與步驟…………………………………………………………………………………………27
3.1 合成 RAFT 試劑(Dibenzyltrithiocarbonate,DBTTC)【35-36】…………………………………………………………27
3.2 核磁共振儀分析(Nuclear Magnetic Resonance Spectroscopy, NMR)………………………………………………30
3.3 微分式掃描熱量分析儀（DSC）實驗步驟……………………………………………30
3.4 熱重/熱示差分析儀(Termal Analyzer)實驗步驟………………………31
3.5 凝膠滲透層析儀(Gel Permeation Chromatograph,GPC)實驗步驟…32
第四章	結果與討論……………………………………………………………………………………………………33
1 RAFT試劑DBTTC之NMR鑑定………………………………………………………………………………33
2  STOBA加入DBTTC之自由基加成聚合反應機制……………………………………37
3  含有DBTTC之BMI-BTA反應動力學……………………………………………………………38
3.1  DBTTC反應放熱對時間關係……………………………………………………………………38
3.2  DBTTC轉化率對時間關係…………………………………………………………………………43
3.3  DBTTC反應速率對時間關係……………………………………………………………………45
3.4  DBTTC反應動力學活化能及頻率因子………………………………………………50
4  BMI與BTA聚合反應在有DBTTC存在下之分子量與熱性質分析…………………………52
第五章	結論……………………………………………………………………………………………………………59
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