臺灣博碩士論文加值系統

中 文 摘 要
Dimethylaminoethyl methacrylate-methyl chloride(DMAEM-MC)的聚合体或共聚合体在工業上應用甚廣，而目前最常用的聚合法是在氧化-還原起始劑存在下進行水溶液自由基聚合反應。但此種方法有些不可避免的缺點。本研究則希望能藉著電聚合法及新起始劑系統徹底解決此類問題。
本研究所發展的起始劑系統是Sn+2/Sn+4和Sn+2-EDTA/Sn+4-EDTA兩種，及利用電聚合方法合成Poly(DMAEM-MC)並與化學聚合方法比較。
本文主要可分成四部份：第一部份為加入Sn+2和EDTA至反應液中進行電聚合反應並與化學方法比較，第二部份是將EDTA加入反應液中而Sn+2則由犧牲陽極法製得，第三部份為直接由犧牲陽極法製得Sn+2並進行聚合反應，第四部份為探討所得成品之長期保存性。
加入Sn+2和EDTA至反應液中，以石墨為電極在定電流的操作條件下，結果發現電聚合速率和化學聚合速率都隨單体濃度、起始劑濃度的增加而增加。但電聚合速率都比同樣反應條件下的化學聚合速率快，顯示于電聚合過程Sn+2有經由電極的作用而再生，因而保持Sn+2在一定的濃度下，促使聚合速率較化學方法為快。實驗結果顯示：電流密度，pHi值和[Sn+2]i/[EDTA]i的比值是三個主要影響因素。欲得聚合體最高分子量之最佳[Sn+2]i/[EDTA]i比值依反應的pHi值而變；當溶液的pHi值高於4.00，則最佳[Sn+2]i/[EDTA]i比為5.00；但當溶液的pHi值低於2.50，則最佳[Sn+2]i/[EDTA]i比為1.00，而在此比值下電聚合所得聚合體分子量可高達1.70x106相對於化學法之2.79×105。在定電流密度之下聚合體分子量與反應時間呈線性關係且當溫度介于35-55℃之間，其分子量增加速率為1.14x105 g/mole-h並且與反應溫度無關，但化學法則無此關係式存在。也就是說，溫度在電聚合中是影響力較小的因素。此是與化學聚合方法最大的差異。至於反應的自由基產生機構則推導如式(1)及式(2)所示：

其中為：-OOC2H4N(CH3)3Cl
於第一部份實驗中Sn+2是預先加入反應液中，如此會造成有些反應是不可控制的。於反應中只加入EDTA而Sn+2則利用犧牲陽極法即時產生，如此的電聚合，更為方便且更易控制反應速率。實驗結果顯示此方法是可行的且攪拌速率，PHi值和電極組合方式明顯地影響轉化率及聚合体分子量，至於溫度的影響因素較小，不明顯，此點電聚合明顯地與化學方法非常不一樣，而單体濃度的影響與化學方法類似。最佳攪拌速率是0 rpm而pHi則是1.75。至於最佳[EDTA]i則隨電聚合時間的增加而增加，反應速率隨電流密度提高而增加，但電流效率則因副反應存在而隨電流密度增加而降低。實驗亦得到較佳的反應溫度與濃度分別是45℃和0.98M。最後並由實驗結果得到其動力學方程式。如式(3)所示。
Rp1=K1 [current density]0.46 [DMAEM-MC]1.85 (3)
其中K1是反應速率常數，其活化能為23.2kJ/mole。
而其適用範圍則是溫度在15至45℃之間，單體起始濃度在0.48
至1.48M之間。
論文之第三部份是利用無共起始劑之犧牲陽極法產生Sn+2來起始反應，如此當可更簡化此電聚合系統。實驗結果顯示攪拌速率、pHi值、電流密度和電極組合方式是影響轉化率和聚合体分子量的主要因素。至於反應溫度和單体濃度對轉化率的影響則相當的不明顯，與化學聚合方法完全不一樣。而對分子量的影響則因黏度效應的存在而顯得較明顯。較佳反應條件是在攪拌速率0 rpm、pH 5.50、反應溫度25℃及單体濃度0.73M。至於電流密度的影響則類似犧牲陽極法。最後並由實驗結果得到其動力學方程式。如式(4)所示。
Rp2=K2 [current density]0.98[DMAEM-MC]0.76 (4)
其中K2是反應速率常數，其活化能為8.90kJ/mole。
而其適用範圍則是溫度在15至45℃之間，單體起始濃度在0.73至1.48M之間。
論文的最後一部份是探討此起始劑系統所得聚合体成品之長期保存性。結果顯示：所得聚合体都有明顯的後聚合反應發生且後聚合轉化率隨保存時間之增加而增加，至於分子量方面則因有解聚合的存在，會達到最高值後緩慢下降至一穩定值，特別是當系統中有EDTA時此現象更明顯。pHi，[Sn+2]i/[EDTA]i 比值及[DMAEM-MC]i三項是影響後聚合的三個主要因素。一般而言，當pHi小於或等于2.50其後聚合在[Sn+2]i/[EDTA]i 為1或2較明顯，但若大於或等于3.25以上則[Sn+2]i/[EDTA]i 之比值在5或10較明顯。至于[DMAEM-MC]i 則是濃度愈高，後聚合愈明顯。化學法，電聚合法及犧牲陽極法所得之最大後聚合分子量都可達1.2×107 ，而無共起始劑之犧牲陽極法可達5.0×106。

英文摘要

The homopolymer or copolymer of dimethylaminoethyl methacrylate- methyl chloride(DMAEM-MC) is very useful in industry. Generally, aqueous polymerization with redox initiators is the most widely used method for producing this type of polymer. However, there are some disadvandges existing in this method which is difficult to modify or overcome. In this dissertation , the problems were solved by using new initiator and new technique of polymerization. Four subjects were probed as follow. 1st, the Sn+2 and EDTA were added to the monomer solution and initiated the polymerization by the electrolysis and chemical methods. Simultaneously, the comparison of the two different methods were also discussed. 2nd, the polymerization was carried out by the sacrifical Sn anode which generated Sn+2 in-situ and the affecting factors of this system were also determined. 3rd, The system was further simplified by using Sn electrodes without any coinitiators, EDTA, i.e. bare anode and the Sn+2 was also generated in-situ. Last, the postpolymerization of the product was examined by the investigation of conversion and polymer molecular weight.
The electropolymerization of DMAEM-MC was carried out in aqueous solution by using Sn+2-EDTA as initiator and graphite as electrodes and the results compared with that of chemical method. The results showed that both the polymerization rates of electrolysis and chemical methods increased with monomer and initiator concentrations. However, at the same operating condition, the polymerization rate of electrolysis method was higher than that of the chemical method. It showed that the Sn+2 ion was generated by the electrode during the electropoly-merization which induced the concentration of Sn+2 to be a constant and resulted the higher polymerization rate comparing to the chemical method. The results indicated that the major factors affecting the molecular weight of the polymer were the pHi value and the [Sn+2]i /[EDTA]i ratio. On the other hand, in the range of 35 to 55℃, the molecular weight increasing rate was 1.14x105 g/mole-h and was independent to temperature. i.e. temperature was the minor factor of the electropolymerization,which was quite different from chemical method. Increasing the pHi values of the electrolyte decreases the polymer molecular weight at fixed operating conditions. The optimum [Sn+2]i /[EDTA]i ratio to obtain the highest polymer molecular weight mainly depended on the pHi value. In the range of higher pHi values, pHi=3.25 or higher , the optimum ratio of [Sn+2]i/[EDTA]i is about 5.00. However,in the range of lower pHi values, pHi=2.50 or lower , the optimum ratio is 1.00. In the electropolymerization, the polymer molecular weight could be controlled easily by current density and the highest molecular weight obtained by the electrolysis method was 1.69x106compared to the 2.97x105 of chemical method. The free radical generation mechanisms were shown in Eqs. (1) and (2)：

where  is -OOC2H4N(CH3)3Cl
The sacrifical Sn anode method was used to make breakthrough of some problems of previous electropolymerization and to simplify the
polymerization system. The results showed that the sacrificial anode
could be used to initiate the monomer system and the major affecting factors were agitation rate, pHi, current density and geometry of electrodes.
On the other hand, temperature was also a minor factor in the range from 25 to 45℃ and the effect of monomer concentration was similar to the
chemical method. The optimum agitation rate, pHi, temperature and monomer concentration were 0 rpm, 1.75, 45℃ and 0.98M, respectively.
The optimum [EDTA]i increased with reaction time, it may be maintained by continous addition of EDTA to the electrolysis during the reaction
time. The reaction rate increased with current density. However, the current efficiency decreased with the increase of current density. The kinetic equation was obtained as shown in Eq. (3)：
Rp1=K1 [current density]0.46 [DMAEM-MC]1.85 (3)
The polymerization was further simplified by only using Sn+2 cation as initiator which was generated in-situ by the bare sacrificial anode method without EDTA. The major factors which affected both the conversion and polymer molecular weight were pHi, current density and assembly of electrodes. On the other hand, temperature was also a minor factor in the range from 25 to 45℃ and the effect of monomer concentration was similar to the chemical method.
The optimum agitation rate, pHi ,temperature and monomer concentration were 0 rpm, 5.50, 25℃ and 0.73M, respectively. The effect of current density was same as that of sacrificial anode. The kinetic equation was obtained as shown in Eq. (4)
Rp2=K2 [current density]0.98[DMAEM-MC]0.76 (4)
The last subject of this dissertation was the study of postpolymeriz-ation. The results showed that all the synthesis methods had showed the postpolymerization apparently. The conversion of postpolymerization
increased with shelf time. However, the molecular weight of postpolymerization might reach a maximum and slowed down
to a stable value. It indicated that the degradation of polymer might
happen during the shelf- time in some runs, especially, in the presence of
much more EDTA. The pHi ,[Sn+2]i/[EDTA]i ratio and [DMAEM-MC]i were the major factors which affected the rate of postpolymerization.
When the pHi was smaller,or equal to ,2.50 and the [Sn+2]i/[EDTA]i ratio was 1.00 or2.00, the postpolymerization was obvious. However, when the pHi was larger,or equal to, 3.25 and the [Sn+2]i/[EDTA]i ratio is 5.00 or 10.0, the postpolymerization was obvious. The results also revealed that the rate of postpolymerization increased with the increase of [DMAEM-MC]i. The stable molecular weight by chemical, electropolymerization and sacrifical anode methods could be as high as 1.20x107 and the stable molecular weight obtained by the sacrificial anode without coinitiator was 5.00x106.

封面
目錄
中文摘要
英文摘要
誌謝
圖目錄
表目錄
符號說明
第一章 前言
1.1 DMAEM-MC的聚合系統與用途
1.2 電聚合之分類
1.2.1 依活性基來源分類
1.2.1.1 經由單體的直接還原或氧化進行電聚合反應
1.2.1.2 間接起始的電聚合反應
1.2.2 依反應機構分類
1.2.2.1 鏈鎖聚合反應
1.2.2.1.1 自由基聚合反應
1.2.2.1.2 陰離子聚合反應
1.2.2.1.3 陽離子聚合反應
1.2.2.1.4 配位聚合反應
1.2.2.2 逐步聚合反應
1.2.2.2.1 Kolbe電解反應
1.2.2.2.2 氧化偶合反應
1.3 電聚合影響因素
1.3.1 電解方法
1.3.1.1 定電流電解
1.3.1.2 定電壓電解
1.3.1.3 電流中斷法
1.3.1.4 電流逆向法
1.3.2 溶劑
1.3.3 電極材料
1.3.4 支持電解質
1.3.5 電解槽設計
1.4 研究動機與本文大綱
第二章 實驗
2.1 藥品與器材
2.1.1 藥品
2.1.2 設備
2.2 實驗裝置
2.3 實驗步驟
2.3.1 聚合物的合成
2.3.1.1 電聚合操作
2.3.1.2 化學聚合操作
2.3.2 聚合體分子量的測量
2.3.3 聚合反應轉化率之算出
2.3.4 FTIR分析
第三章 以Sn-EDTA為起始劑電聚合竹水應與化學聚合反應
3.1 前言
3.2 結果與討論
3.2.1 [Sn]/[EDTA]比值的影響
3.2.2 電流密度的影響
3.2.3 反應時間的影響
3.2.4 反應溫度的影響
3.2.5 [Sn]/[EDTA]比值的影響
3.2.6 pH的影響
3.2.7 起始劑濃度的影響
3.2.8 [DMAEM-MC]的影響
3.2.9 反應機構的探討
3.2.9.1 化學聚合之反應機構
3.2.9.2 含Sn離子之電聚合之反應機構
3.3 結論
第四章 以犧牲陽極進行聚合反應
4.1 前言
4.2 結果與討論
4.2.1 攪拌速率的影響
4.2.2 pH的影響
4.2.3 電流密度的影響
4.2.4 [EDTA]影響
4.2.5 陰極面積的影響
4.2.6 溫度的影響
4.2.7 [DMAEM-MC]的影響
4.2.8 犧牲陽極法與其他方法的比較
4.2.9 犧牲陽極法聚合反應之反應機構
4.3 實驗結果之動力學方程式
4.4 結論
第五章 無共起始劑之犧牲陽極法
5.1 前言
5.2 結果與討論
5.2.1 攪拌速率的影響
5.2.2 pH的影響
5.2.3 電流密度的影響
5.2.4 陰極面積的影響
5.2.5 溫度的影響
5.2.6 [DMAEM-MC]的影響
5.2.7 無共起始劑之犧牲陽極法聚合反應之反應機構
5.3 實驗結果之動力學方程式
5.4 結論
第六章 後聚合反應
6.1 前言
6.2 結果與討論
6.2.1 以Sn-EDTA為起始劑的電聚合法與化學法與的後聚合反應
6.2.1.1 [Sn]/[EDTA]比值的影響
6.2.1.2 電流密度的影響
6.2.1.3 pH的影響
6.2.1.4 保存時間的影響
6.2.1.5 溫度的影響
6.2.1.6 起始劑濃度的影響
6.2.1.7 [DMAEM-MC]的影響
6.2.2 犧牲陽極法之後聚合反應
6.2.2.1 攪拌速率的影響
6.2.2.2 pH的影響
6.2.2.3 電流密度的影響
6.2.2.4 [EDTA]影響
6.2.2.5 陰極面積的影響
6.2.2.6 溫度的影響
6.2.2.7 [DMAEM-MC]的影響
6.2.3 無共起始劑之 犧牲陽極法之後聚合反應
6.2.3.1 攪拌速率的影響
6.2.3.2 pH的影響
6.2.3.3 電流密度的影響
6.2.3.4 陰極面積的影響
6.2.3.5 溫度的影響
6.2.3.6 [DMAEM-MC]的影響
6.3 結論
第七章 綜合討論，結論與未來工作建議
7.1 綜合討論
7.2 結論
7.3 未來工作建議
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自述
著作
附錄

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