Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3254
標題: 蒙脫土接枝改質氯甲基苯乙烯/苯乙烯共聚合高分子製備 Pickering 乳液
Pickering Emulsions Prepared by Modified Vinylbenzyl Chloride/Styrene Copolymers Grafted on MMT Surface
作者: 陳銘宏
Chen, Ming-Hong
關鍵字: 蒙脫土;MMT;氯甲基苯乙烯;苯乙烯;皮克林乳液;vinylbenzyl chloride;styrene;Pickering emulsion
出版社: 化學工程學系所
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摘要: 
本研究方向是以高分子改質蒙脫土製備表面具備部份親水及部份親油性,並以此改質蒙脫土當Pickering乳液之界面劑進行乳化,乳液中油相為甲苯或1, 6–己二醇二丙烯酸酯(1,6-Hexanediol diacrylate, HDDA),觀察乳化現象、粒徑、型態及相反轉行為。
改質蒙脫土以吸附微胞聚合製備,使用含乙烯基界面劑 vinyl benzyl dimethyl dodecyl ammonium chloride (VBDDAC)及十六烷基三甲基溴化銨(cetyl trimethyl ammonium bromide, CTAB)混合吸附微胞,在將加入含乙烯基單體如氯甲基苯乙烯(vinylbenzyl chloride, VBC)或苯乙烯(styrene, S)聚合形成接枝高分子,其中接枝高分子有兩個系統,系統(I)為表面聚合不同重量比氯甲基苯乙烯/苯乙烯共聚物P(VBC-ST),並以二甲基乙醇胺(dimethyl ethanol amine, DMEA)銨化(quaterization)共聚物中VBC鏈段,使其由親油性轉為親水性,得到表面部份親水部份親油構造之蒙脫土P(VBCQ-S);系統(II)為表面聚合PVBC,再作不同莫爾百分比之銨化,得到部份親油PVBC及部份親水PVBCQ之蒙脫土P(VBC-VBCQ);由靜態接觸角分析得知,系統(I)與水接觸角度隨苯乙烯在共聚物中重量分率增加而增加,角度介於19~80 o間,系統(II)與水接觸角度隨銨化量減少而增加,角度介於20~75 o間。
以系統(I)改質蒙脫土Pickering乳化甲苯/水,在P(VBCQ-S)共聚物重量比為4/0及3/1蒙脫土因表面較親水,其乳液為O/W,而0/4較親油則乳液為W/O,其2/2、1/3之改質蒙脫土則無法乳化;系統(II)改質蒙脫土所製備之乳液油相有分兩種,為甲苯或HDDA,在甲苯/水的乳化中,P(VBC-VBCQ) 25/75及50/50 %所製備乳液為O/W,其PVBCQ 75/25及90/10 %則無法乳化;在HDDA/水的乳化中全成份範圍皆可乳化,P(VBC-VBCQ) 25/75、50/50及75/25% 乳液為O/W,而P(VBC-VBCQ) 90/10 %為W/O,且當油相從甲苯替換成HDDA後,於相同乳化條件下,乳液粒徑皆變小。
由FITR分析可發現HDDA與PVBC混合後,其PVBC結構中C-Cl 拉伸震動峰位置從1265 cm-1 位移至1274 cm-1,且HDDA中C=O拉伸震動峰位置從1729 cm-1位移至1724 cm-1,表示兩者具分子間作用力或相容性使乳液粒徑變小。
最後,選取系統(II)改質蒙脫土所製備W/H (water in HDDA) Pickering乳液以紫外光聚合法製備交聯亞克力薄膜,由SEM分析發現交聯乳液界面包覆著片狀改質蒙脫土,證實改質蒙脫土的確存在於油
水界面之中。

The aim of this study is to prepare modified MMT by surface grafting polymer on MMT surface for Pickering emulsions preparation to obtain O/W or W/O emulsions. The modified MMT bears partially hydrophobic and partially hydrophilic characters that are suitable for oil/water or water/oil emulsions. Toluene or 1, 6-hexanediol diacrylate (HDDA) were applied as oil phase in this study. The emulsion diameter, morphology and phase inversion behavior were investigated with respect to the different polymers grafted on MMT surface.
Modification of MMT was done initially to form bilayer micelles on MMT surface using vinylbenzyl dimethyl dodecyl ammonium chloride (VBDDAC) and cetyltrimethyl ammonium bromide (CTAB) by cation exchange. Then, we added vinyl-containing monomers, such like vinylbenzyl chloride (VBC) or styrene (S), following by polymerization on MMT surface by ad-micellar polymerization. Two kinds of grafted polymers were synthesized. Polymer (I) is vinylbenzyl chloride/styrene copolymer P(VBC-S) with different weight ratios, followed by quaternizing PVBC chains with dimethyl ethanol amine (DMEA) and obtained P(VBCQ-S) copolymer with partially hydrophilic and partially hydrophobic characters. Polymer (II) is to graft PVBC, then quaternized PVBC chains by varying moles of DMEA to obtain P(VBC-VBCQ) grafted on MMT bearing partially hydrophobic and partially hydrophilic characters. Static water contact angle measurements show the contact angles for Polymer P(VBCQ-S) increases with increasing styrene fraction and is between 19 to 80 o. For Polymer P(VBC-VBCQ), the contact angle decreases with the increasing DMEA reacted and are between 20 to 75 o.
Pickering emulsions were prepared by P(VBCQ-S) modified MMT which were used as emulsifier of toluene and water, and we found that O/W emulsions were formed by P(VBCQ-S) copolymer with the weight ratio of VBC to styrene between 4/1 and 3/1 due to their hydrophilic charater. The W/O emulsions were obtained at weight ratio of 0/4. However, there are no stable emulsions formed for P(VBCQ-S) at 2/2 and 3/1 ratios. Two model oils were used including toluene and 1, 6-hexanediol diacrylate (HDDA) to prepare emulsions by using polymer P(VBC-VBCQ) as emulsifier. When toluene and water were emulsified, it was found O/W emulsions were formed for P(VBC-VBCQ) at 25/75 or 50/50, but P(VBC-VBCQ) at 75/25 and 90/10 did not form stable emulsions. polymer P(VBC-VBCQ) is applied to HDDA and water emulsions, and O/W emulsions were formed by P(VBC-VBCQ) at 25/75、50/50、75/25. The W/O emulsions was obtained for P(VBC-VBCQ) at 90/10. Furthermore, emulsions diameter is smaller as oil phase toluene was replaced with HDDA at same emulsified condition. This is explained by molecular interactions for C-Cl in PVBC and C=O in acrylate.
FTIR showed the C-Cl wagging vibration of PVBC shifts from 1265 to 1274 cm-1 and the C=O stretching vibration of HDDA shifts from 1729 to 1724 cm-1 after mixing of these two components and indicated that there is molecular interaction or partial compatibility between PVBC and
HDDA.
Finally, solid Pickering films were produced by UV-polymerization of HDDA phases in W/H emulsions using polymer P(VBC-VBCQ) at 90/10 as emulsifier. SEM reveals that modified MMT exists on the interface
of water and HDDA.
URI: http://hdl.handle.net/11455/3254
其他識別: U0005-2207201316381000
Appears in Collections:化學工程學系所

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