臺灣博碩士論文加值系統

本研究於SDS / SMA安定之迷你乳化聚合反應系統，加入一低分子量、不溶於水的染料（Blue 70）做為探針分子，探討溫度、單體親疏水性、不同單體共聚合、少量添加劑（5 wt % 之短鏈醇、親水性單體）對迷你乳化聚合反應之動力、成核機構之影響。使SDS 濃度 ( [SDS] = 5 mM ) 低於臨界微胞濃度（CMC = 8.2 mM），排除微胞成核機構的可能。實驗結果歸納如下：
MMA、ST、MMA-ST ( 50：50 w / w ) 之系統，提高反應溫度，聚合反應速率及自由基裂解速率均提高。不同溫度下，單體液滴成核在ST的系統均扮演重要的角色，且溫度上升會使 Pdye 值上升，即升溫會加速單體液滴成核。升溫也加強 MMA 反應系統之單體油滴成核效應，但其 Pdye 值 ( 5∼25 % ) 與ST系列 ( 60∼98 % ) 相比仍相當低，由此說明水相成核機構在MMA迷你乳化聚合反應中扮演較重要的角色。在 MMA-ST ( 50：50 w / w ) 的系統，提高溫度會使 Pdye 值下降，顯示 MMA 單體對溫度更為敏感，升溫加速 MMA 單體的聚合速率，使水相成核更為重要。
四種單體極性高至低排列為MMA、BMA、BA、ST，單體極性愈高，Pdye 數值愈低，顯示單體極性愈低，單體液滴成核機構愈重要。
MMA、ST單體不同比例混合，若單體組成中 MMA 比例愈
高，聚合反應速率愈快、乳漿粒子粒徑愈小，而Pdye 值則愈小。
MMA-ST 共單體的系統，反應初期是以 MMA 為主的水相均
質成核扮演較重要的角色。X > 40 % 後，ST單體大量反應，
使油相成核變得重要。
少量（5 %）親水性單體MMA或EtOH加入ST迷你乳化反應系統，均使聚合反應速率變快、乳漿粒子粒徑分佈更均一。加入等量的 MMA、EtOH ， MMA 對提高系統水相成核有較顯著的效果。

The effect of temperature , monomer polarity, MMA-ST co-monomer , 5% wt ratio additive ( such as MMA , EtOH ) on kinetics and particle nucleation mechanisms in miniemulsion were investigated by using a water-insoluble dye (blue-70) as the probe molecule. According to above principle to make SDS concentration ( [SDS] = 5 mM ) lower then CMC （CMC = 8.2 mM）and except the probability of micellar nucleation. The results are shown below：
In MMA , ST , MMA-ST ( 50：50 w / w ) miniemulsion , polymerization rate and decomposition rate of free-radicals are both in proportion to temperature increases . Monomer droplet nucleation play an important role in ST miniemulsion with different temperature . Pdye will increase when the temperature raising up. In another word, monomer droplet nucleation will be formulated in a short period by increasing the temperature. Moreover, raising temperature also enhances monomer droplet nucleation in MMA miniemulsion. However, the compare with Pdye ( MMA：5∼25 % , ST： 60∼98 % ) are extremely low. According these results, homogeneous nucleation is a major factor in MMA miniemulsion. In MMA-ST ( 50：50 w / w ) miniemulsion ; Pdye will decrease when the temperature are raising up which shows the sensitive of temperature of MMA , Raising up the temperature will increase the importance of homogeneous nucleation and MMA polymeration rate .
MMA is the most hydrophilic , BMA is next , and ST
is the most hydrophobic among MMA , BMA , BA , ST. The hydrophility of monomer increased, Pdye decreased. It show that monomers with lower polarity , monomer droplet nucleation is more important.
MMA-ST mixed in different proportion,polymeration
rate increased and latex particle diameter decreased with
MMA amount ( wt ratio ) increase , however Pdye reduced
with MMA increase. Homogeneous nucleation play an
important role in the initial stage of polymerization. As
X .> 40 % , monomer droplet nucleation is significant due
to ST polymerization on large scale.
In ST miniemulsion , polymerization rate increase and latex paticle size distribution will become uniform with a small amount additive ( 5 % wt ratio of MMA, EtOH ) . The same amount of MMA,EtOH addition , MMA will cause a remarkable promotion of homogeneous nucleation.

本研究於SDS / SMA安定之迷你乳化聚合反應系統，加入一低分子量、不溶於水的染料（Blue 70）做為探針分子，探討溫度、單體親疏水性、不同單體共聚合、少量添加劑（5 wt % 之短鏈醇、親水性單體）對迷你乳化聚合反應之動力、成核機構之影響。使SDS 濃度 ( [SDS] = 5 mM ) 低於臨界微胞濃度（CMC = 8.2 mM），排除微胞成核機構的可能。實驗結果歸納如下：
MMA、ST、MMA-ST ( 50：50 w / w ) 之系統，提高反應溫度，聚合反應速率及自由基裂解速率均提高。不同溫度下，單體液滴成核在ST的系統均扮演重要的角色，且溫度上升會使 Pdye 值上升，即升溫會加速單體液
第一章 緒論…………………………………………………………… 1
1-1 乳液……………………………………………………. 1
1-1-1 簡介……………………………………………. 1
1-1-2 乳液之分類…………………………………….2
1-2 乳化聚合反應 ……………………………………...…4
1-2-1 簡介…………………………………………….4
1-2-2 自由基加成聚合反應…………………………6
1-2-3 乳化聚合反應之應用…………………………8
1-3 研究背景及目的……………………………………..………9
第二章 文獻回顧………………………………………………………11
2-1 粒子核心形成機構………………………………………… 11
2-1-1 微胞成核理論 ( micellar nucleation )……………. 11
2-1-2 均質成核理論 ( homogeneous nucleation )……… 13
2-1-3 凝聚成核理論 ( coagulative nucleation )……….. 14
2-1-4 單體液滴成核理論 ( monomer droplet nucleation )
………………………………………….. 15
2-2 迷你乳液之安定性……………………………………. 15
2-2-1 奧斯瓦老化效應…………………………….. 15
2-2-2 滲透壓效應……………………………………. .17
2-2-3 凝聚 ( flocculation ) 與合併 ( coalecence ) ….. .19
2-3 迷你乳液及迷你乳化聚合反應之文獻回顧………………19
第三章 實驗儀器及方法……………………………….……………..32
3-1 實驗用原料………………………………….…………..….32
3-2 儀器及實驗裝置…………………………….……………...33
3-2-1 雷射光粒徑分析系統 (laser particle size
analyzing system；LPA)……...…………………..33
3-2-2 其它儀器………………………….………...34
3-2-3 乳化聚合反應設備………………………….34
3-3 實驗方法……………………………………………...35
3-3-1 SMA純化…………...………………….…..35
3-3-2 稀釋液的配製……………………….……..35
3-3-3 迷你乳液的製備…………… ………….…36
3-3-4 油滴粒徑的量測…………………………..36
3-3-5 批次迷你乳化聚合反應實驗..…………..36.
3-3-6 以TEM量測迷你乳漿粒子直徑………..37
3-3-7 乳漿樣品中染料（Blue 70）含量之測量.
…………………………………38
3-4 實驗數據之處理……………………………………..40
3-4-1 迷你乳化聚合反應轉化率之量測………….40
3-4-2 反應前單體液滴數之計算……………….….41
3-4-3 在不同轉化率下乳漿產品粒子數之計算….41
3-4-4 在不同轉化率下平均膠體粒子數之計算….42
3-4-5 在不同轉化率下單體液滴數之計算…………….42
3-4-6 乳漿產品中染料（Blue 70）含量之計算………42
3-4-7 藉由單體液滴及水相成核所產生乳漿
粒子數之計算………………………………43
第四章 結果與討論……………………………………………..57
4-1 溫度對 MMA、ST、MMA-ST ( 50：50 w / w )
迷你乳化聚合反應之反應動力學、粒子成核機
構的影響……………………………………………….57
4-1-1 動力學數據……………..…………………………58
4-1-2 對Pdye 的影響…………..…………….…………..59
4-1-3 對聚合體粒子數及粒子成核機構之影響…..61
4-2 單體親疏水性（MMA、BMA、BA、ST ）對迷你
乳化聚合反應之反應動力學、粒子成核機構的影響….74
4-2-1 動力學數據………………….…………………….74
4-2-2 對Pdye的影響………………………………….…..74
4-3 探討MMA、ST單體不同比例混合對迷你乳化
共單體聚合反應之反應動力學、粒子成核機構的
影響……………………………………………………….78
4-3-1 動力學數據………………………………….…….78
4-3-2 對Pdye的影響……………………………………...78
4-3-3 對聚合體粒子及單體油滴數目的影響…….....….79
4-4 探討少量添加劑（5 wt % 之短鍊醇EtOH、親
水性單體MMA）對迷你乳化共單體聚合反應之
反應動力學、粒子成核機構的影響…………………….85
4-4-1 動力學數據………………………………….…….85
4-4-2 對Pdye的影響……………………………………...86
4-4-3 對聚合體粒子及單體油滴數目的影響…….....….86
第五章 結論…………………………………………………………...91
參考文獻……………………………………..…………………….…..94
附錄…………………………………………………………………….99

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