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以超臨界二氧化碳流體聚合氮-異丙基丙烯醯胺之動力學研究 = Kineti...

國立高雄大學化學工程及材料工程學系碩士班

以超臨界二氧化碳流體聚合氮-異丙基丙烯醯胺之動力學研究 = Kinetics of N-isopropylacrylamide Polymerizations in Supercritical Carbon Dioxide Fluids

紀錄類型:	書目-語言資料,印刷品 : 單行本
並列題名:	Kinetics of N-isopropylacrylamide Polymerizations in Supercritical Carbon Dioxide Fluids
作者:	趙崇亨,
其他團體作者:	國立高雄大學
出版地:	[高雄市]
出版者:	撰者;
出版年:	民100
面頁冊數:	94葉圖，表格 : 30公分;
標題:	2'2-偶氮雙異丁睛
標題:	N-isopropylacrylamide
電子資源:	http://handle.ncl.edu.tw/11296/ndltd/14746292294001336150
附註:	參考書目：葉76-82
摘要註:	本研究是以超臨界二氧化碳流體(supercritical carbon dioxide，scCO2)來聚合氮-異丙基丙烯醯胺(N-isopropylacrylamide，NIPAAm)，探討其聚合動力學及反應機制。以scCO2聚合NIPAAm前，本研究先以高壓示差掃瞄熱卡計(high-pressure differential scanning calorimeter，HP DSC)調查CO2與NIPAAm及起始劑(2,2'-偶氮雙異丁睛，AIBN)之間是否有交互作用力，可幫助熔解。調查結果發現在CO2環境下，壓力越高，NIPAAm及AIBN的熔點越低，其熔解焓也伴隨著下降，而在N2環境下，熔點並不會隨壓力而有明顯改變，證明了CO2與NIPAAm及AIBN之間存在著交互作用力，CO2壓力愈高，CO2密度愈高，交互作用力愈強，NIPAAm及AIBN熔點越低。接著以甲醇(methanol，MeOH)將NIPAAm/AIBN混合均勻並完全蒸發MeOH後，於HP DSC中，恆溫55 oC，CO2的壓力2.72MPa、3.04MPa或4.08MPa(此三壓力下，NIPAAm熔點低於55 oC)，以調查NIPAAm是否會聚合反應。調查結果發現NIPAAm可在CO2中聚合反應。為探討NIPAAm在scCO2中(使用高壓反應釜)聚合反應之動力學，本研究同時比較NIPAAm在MeOH中之聚合反應。實驗結果發現，在MeOH中的起始反應比在scCO2的起始反應快了約3個小時，但NIPAAm在MeOH中的轉化率卻較scCO2者低；實驗結果，在MeOH中聚合動力式為R"p"=k"1" [M]^1.2655 [I]^0.5075，在scCO2中聚合速率式為R"p"=k〖"2" [M]〗^1.4993 [I]^0.8135，[M] 是單體濃度，[I] 是起始劑濃度；顯然地，MeOH中的聚合速率動力式較接近理論的聚合速率動力式(Rp = k[M][I]0.5)，即聚合成長步驟約是一個單體分子與一個自由基分子相碰撞反應使分子量成長，即聚合成長速率式是Rp = kp[M][R・]，[R・] 是自由基總濃度，但在scCO2中由聚合速率，可推想聚合成長步驟是1.5個單體分子與1.63個高分子自由基分子同時相碰撞反應使分子量成長，即聚合成長速率式是Rp = kp[M]1.5[R・]1.63，此高的速率式級數可能是在scCO2中的單體分子及高分子自由基分子的高擴散速率所導致的。將聚合出的PNIPAAm測其平均分子量，發現同樣的單體及自由基濃度及同樣的聚合成長時間(從起始反應開始算起)，在scCO2中聚合NIPAAm之平均分子量最高可達120萬g/mol，而在MeOH中聚合NIPAAm之平均分子量最高只達35萬g/mol，可能的原因包括(1) 反應後期在scCO2中單體仍有較高的擴散速率與高分子自由基分子反應，(2) 在scCO2中高分子自由基分子較易發生結合式的終止反應(combination termination)而不易發生不均勻式的終止反應(disportionation termination)，(3) 在scCO2中高分子自由基壽命較長。 In this study, polymerization kinetics of N-isopropylacrylamide (NIPAAm) in supercritical carbon dioxide (scCO2) was investigated. A high-pressure differential scanning calorimeter (HP DSC) was first used to investigate whether high pressure CO2 could assist melting of NIPAAm and 2,2’-Azobis(isobutyronitrile) (AIBN) as an initiator. HP DSC data found that NIPAAm and AIBN melted in high pressure CO2 at 55 oC at which the polymerization could occur. The melting points of NIPAAm and AIBN both decreased with increasing CO2 pressure. The NIPAAm polymerization in scCO2 was compared with that in methanol (MeOH). It was found that the initial rate in MeOH was faster than that in scCO2, but the final conversion of NIPAAm in MeOH was lower than that in scCO2. The polymerization rate (Rp) equation in MeOH was Rp = k1[M]1.2655[I]0.5075 and in scCO2 was Rp = k2[M]1.4993 [I]0.8135, where [M] was the monomer concentration and [I] the initiator concentration. Apparently, the polymerization rate equation in MeOH was closer to the theoretical equation (Rp = k[M][I]0.5). This suggested that the polymerization mechanism in scCO2 involved more than one monomer molecule collided with more than one radical in the propagation step, attributed to high diffusion rates of monomer and radical in scCO2. For a given [M] and [I], the average molecular weight of PNIPAAm from the polymerization in scCO2 was about 3 times higher than that in MeOH. This could be attributed to three possible reasons: (1) for the reaction in the latter stage, the monomer and radicals were higher in diffusion rate in scCO2, (2) the polymer radicals in scCO2 were easier to conduct the combination termination other than the disportionation termination, and (3) the polymer radicals had longer life in scCO2.

以超臨界二氧化碳流體聚合氮-異丙基丙烯醯胺之動力學研究 = Kinetics of N-isopropylacrylamide Polymerizations in Supercritical Carbon Dioxide Fluids
趙, 崇亨

以超臨界二氧化碳流體聚合氮-異丙基丙烯醯胺之動力學研究 = Kinetics of N-isopropylacrylamide Polymerizations in Supercritical Carbon Dioxide Fluids / 趙崇亨撰 - [高雄市] : 撰者, 民100. - 94葉 ; 圖，表格 ; 30公分.
參考書目：葉76-82.
2'2-偶氮雙異丁睛N-isopropylacrylamide

以超臨界二氧化碳流體聚合氮-異丙基丙烯醯胺之動力學研究 = Kinetics of N-isopropylacrylamide Polymerizations in Supercritical Carbon Dioxide Fluids
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330 $a 本研究是以超臨界二氧化碳流體(supercritical carbon dioxide，scCO2)來聚合氮-異丙基丙烯醯胺(N-isopropylacrylamide，NIPAAm)，探討其聚合動力學及反應機制。以scCO2聚合NIPAAm前，本研究先以高壓示差掃瞄熱卡計(high-pressure differential scanning calorimeter，HP DSC)調查CO2與NIPAAm及起始劑(2,2'-偶氮雙異丁睛，AIBN)之間是否有交互作用力，可幫助熔解。調查結果發現在CO2環境下，壓力越高，NIPAAm及AIBN的熔點越低，其熔解焓也伴隨著下降，而在N2環境下，熔點並不會隨壓力而有明顯改變，證明了CO2與NIPAAm及AIBN之間存在著交互作用力，CO2壓力愈高，CO2密度愈高，交互作用力愈強，NIPAAm及AIBN熔點越低。接著以甲醇(methanol，MeOH)將NIPAAm/AIBN混合均勻並完全蒸發MeOH後，於HP DSC中，恆溫55 oC，CO2的壓力2.72MPa、3.04MPa或4.08MPa(此三壓力下，NIPAAm熔點低於55 oC)，以調查NIPAAm是否會聚合反應。調查結果發現NIPAAm可在CO2中聚合反應。為探討NIPAAm在scCO2中(使用高壓反應釜)聚合反應之動力學，本研究同時比較NIPAAm在MeOH中之聚合反應。實驗結果發現，在MeOH中的起始反應比在scCO2的起始反應快了約3個小時，但NIPAAm在MeOH中的轉化率卻較scCO2者低；實驗結果，在MeOH中聚合動力式為R"p"=k"1" [M]^1.2655 [I]^0.5075，在scCO2中聚合速率式為R"p"=k〖"2" [M]〗^1.4993 [I]^0.8135，[M] 是單體濃度，[I] 是起始劑濃度；顯然地，MeOH中的聚合速率動力式較接近理論的聚合速率動力式(Rp = k[M][I]0.5)，即聚合成長步驟約是一個單體分子與一個自由基分子相碰撞反應使分子量成長，即聚合成長速率式是Rp = kp[M][R・]，[R・] 是自由基總濃度，但在scCO2中由聚合速率，可推想聚合成長步驟是1.5個單體分子與1.63個高分子自由基分子同時相碰撞反應使分子量成長，即聚合成長速率式是Rp = kp[M]1.5[R・]1.63，此高的速率式級數可能是在scCO2中的單體分子及高分子自由基分子的高擴散速率所導致的。將聚合出的PNIPAAm測其平均分子量，發現同樣的單體及自由基濃度及同樣的聚合成長時間(從起始反應開始算起)，在scCO2中聚合NIPAAm之平均分子量最高可達120萬g/mol，而在MeOH中聚合NIPAAm之平均分子量最高只達35萬g/mol，可能的原因包括(1) 反應後期在scCO2中單體仍有較高的擴散速率與高分子自由基分子反應，(2) 在scCO2中高分子自由基分子較易發生結合式的終止反應(combination termination)而不易發生不均勻式的終止反應(disportionation termination)，(3) 在scCO2中高分子自由基壽命較長。 In this study, polymerization kinetics of N-isopropylacrylamide (NIPAAm) in supercritical carbon dioxide (scCO2) was investigated. A high-pressure differential scanning calorimeter (HP DSC) was first used to investigate whether high pressure CO2 could assist melting of NIPAAm and 2,2’-Azobis(isobutyronitrile) (AIBN) as an initiator. HP DSC data found that NIPAAm and AIBN melted in high pressure CO2 at 55 oC at which the polymerization could occur. The melting points of NIPAAm and AIBN both decreased with increasing CO2 pressure. The NIPAAm polymerization in scCO2 was compared with that in methanol (MeOH). It was found that the initial rate in MeOH was faster than that in scCO2, but the final conversion of NIPAAm in MeOH was lower than that in scCO2. The polymerization rate (Rp) equation in MeOH was Rp = k1[M]1.2655[I]0.5075 and in scCO2 was Rp = k2[M]1.4993 [I]0.8135, where [M] was the monomer concentration and [I] the initiator concentration. Apparently, the polymerization rate equation in MeOH was closer to the theoretical equation (Rp = k[M][I]0.5). This suggested that the polymerization mechanism in scCO2 involved more than one monomer molecule collided with more than one radical in the propagation step, attributed to high diffusion rates of monomer and radical in scCO2. For a given [M] and [I], the average molecular weight of PNIPAAm from the polymerization in scCO2 was about 3 times higher than that in MeOH. This could be attributed to three possible reasons: (1) for the reaction in the latter stage, the monomer and radicals were higher in diffusion rate in scCO2, (2) the polymer radicals in scCO2 were easier to conduct the combination termination other than the disportionation termination, and (3) the polymer radicals had longer life in scCO2.
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610 0 $a 2'2-偶氮雙異丁睛 $a 氮-異丙基丙烯醯胺 $a 超臨界二氧化碳流體 $a 高壓示差掃瞄熱卡計
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