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氮-異丙基丙烯醯胺及丙烯酸在超臨界二氧化碳流體中共聚合之研究 = Cop...

國立高雄大學化學工程及材料工程學系碩士班

氮-異丙基丙烯醯胺及丙烯酸在超臨界二氧化碳流體中共聚合之研究 = Copolymerizations of N-isopropylacrylamide and Acrylic Acid 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:	Copolymerizations of N-isopropylacrylamide and Acrylic Acid in Supercritical Carbon Dioxide Fluids
作者:	陳柏宏,
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:	2014[民103]
面頁冊數:	118面圖，表 : 30公分;
標題:	超臨界二氧化碳
標題:	Supercritical CO2
電子資源:	http://handle.ncl.edu.tw/11296/ndltd/05603109179536436459
附註:	參考書目：面96-106
附註:	103年12月16日公開
摘要註:	本研究以超臨界二氧化碳流體(supercritical carbon dioxide, scCO2)為溶劑，偶氮二異丁腈(azobisisobutyronitrile, AIBN)為起始劑，在55 ℃, 4000 psi下進行氮-異丙基丙烯醯胺(N-isopropylacrylamide, NIPAAm)和丙烯酸(acrylic acid, AA)的共聚合反應的研究。並同時於相同溫度下，以甲醇(methanol, MeOH)為溶劑進行反應，比較兩者之間的差異。在進行NIPAAm和AA的共聚合研究之前，我們先研究NIPAAm的均聚合研究，我們發現NIPAAm在scCO2中的反應速率比在MeOH中慢，但聚合度較高，在scCO2中所聚合的PNIPAAm分子量最高可達120萬，而在甲醇中所聚合的最高分子量只有30萬。凝膠滲透層析儀(gel permeation chromatography, GPC)不適合用來量測PNIPAAm的分子量，GPC所量測出的分子量會遠小於真實的分子量，並會隨分子量越高誤差會越大，可能因為PNIPAAm在四氫氟喃(THF)溶液中分子間或內氫鍵的作用力，在GPC高壓下會使PNIPAAm於溶液中團聚所致。MeOH中所聚合的低分子量的PNIPAAm在水溶液中，和水之間的氫鍵作用力可能大於scCO2中所聚合的PNIPAAm，以致於MeOH中所聚合的低分子量的PNIPAAm的較低溶解溫度(lower critical solution temperature, LCST)會略高於scCO2中所聚合的。而NIPAAm和AA在scCO2和甲醇中的共聚合反應，發現scCO2中所聚合的共聚物的產率和分子量都會低於甲醇中的，scCO2中的共聚合產率會隨NIPAAm/AA的進料莫爾比下降而下降。NIPAAm和AA在scCO2和MeOH中的共聚合反應都是屬於有恆比點(azeotropic composition)的共聚合反應，scCO2中所聚合的共聚物中AA的含量會少於甲醇中所聚合的，並且共聚物中AA的含量會隨反應壓力下降(2000~4000 psi)而增加。兩溶液中的共聚物的Tg會隨AA含量的增加先上升後下降，甲醇中的共聚物在酸性和鹼性溶液中於室溫下成膜，其Tg會高於在中性溶液中成膜的。在scCO2中所聚合的共聚物的LCST都會小於甲醇中所聚合的。最後我們在MeOH和scCO2中的NIPAAm的均聚合反應中添加多壁奈米碳管(multiwall carbon nanotube, MWCNT)，發現MWCNT會清除自由基，提高均聚物PNIPAAm的分子量。在scCO2中，自由基的清除率高達約90% (四小時的反應時間，分子量從37萬提高到116萬 g/mol)，在MeOH中只有51% (四小時的反應時間，分子量從28萬提高到40萬 g/mol)，可能由於scCO2的高擴散能力，使自由基與MWCNT的碰撞機會提高所致。 In this study, the free-radical copolymerizations of N-isopropylacrylamide (NIPAAm) and acrylic acid (AA) in supercritical carbon dioxide (scCO2) utilizing azobisisobutyronitrile (AIBN) as a free radical initiator were investigated. The copolymerizations of NIPAAm and AA in scCO2 were also compared with those in methanol (MeOH). In the absence of AA, the polymerization rate of NIPAAm in scCO2 was slower than that in MeOH whereas the degree of polymerization in scCO2 was higher than that in MeOH. The highest molecular weight of PNIPAAm polymerized in scCO2 was 1.2 million g/mol, but that of PNIPAAm polymerized in MeOH was only 0.3 million g/mol. Gel permeation chromatography (GPC) was not suitable for the characterization of high molecular weight PNIPAAm. PNIPAAm of lower molecular weights (MWs) gave more significant hydrogen-bonding interactions with water and thus exhibited higher LCST (lower critical solution temperature) for PNIPAAm polymerized in MeOH. Yields and MWs of the copolymers polymerized in scCO2 were lower than that polymerized in MeOH, with the yields decreasing with increasing feed of AA. The mole fraction of AA in the copolymer polymerized in scCO2 was lower than that polymerized in MeOH, and the mole fraction of AA in the copolymer polymerized in scCO2 was increasing with decreasing pressure of scCO2 in the range of 2000 to 4000 psi. The glass transition temperature (Tg) of the copolymer was increasing with increasing content of AA in the NIPAAm-rich copolymers but decreasing with increasing content of AA in the AA-rich copolymers. The Tg of the copolymer film formed in alkaline or acidic aqueous solution was higher than that in neutral aqueous solution. Finally, multiwalled carbon nanotubes (CNT) was found to retard polymerizations of NIPAAm but bring about an increase in MWs of PNIPAAm in both scCO2 and MeOH, with the effects of CNT more significant in scCO2 than in MeOH. This can be associated with the loss of radicals due to being scavenged by CNT in the polymerizations of NIPAAm.

氮-異丙基丙烯醯胺及丙烯酸在超臨界二氧化碳流體中共聚合之研究 = Copolymerizations of N-isopropylacrylamide and Acrylic Acid in Supercritical Carbon Dioxide Fluids
陳, 柏宏

氮-異丙基丙烯醯胺及丙烯酸在超臨界二氧化碳流體中共聚合之研究 = Copolymerizations of N-isopropylacrylamide and Acrylic Acid in Supercritical Carbon Dioxide Fluids / 陳柏宏撰 - [高雄市] : 撰者, 2014[民103]. - 118面 ; 圖，表 ; 30公分.
參考書目：面96-106103年12月16日公開.
超臨界二氧化碳Supercritical CO2

氮-異丙基丙烯醯胺及丙烯酸在超臨界二氧化碳流體中共聚合之研究 = Copolymerizations of N-isopropylacrylamide and Acrylic Acid in Supercritical Carbon Dioxide Fluids
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330 $a 本研究以超臨界二氧化碳流體(supercritical carbon dioxide, scCO2)為溶劑，偶氮二異丁腈(azobisisobutyronitrile, AIBN)為起始劑，在55 ℃, 4000 psi下進行氮-異丙基丙烯醯胺(N-isopropylacrylamide, NIPAAm)和丙烯酸(acrylic acid, AA)的共聚合反應的研究。並同時於相同溫度下，以甲醇(methanol, MeOH)為溶劑進行反應，比較兩者之間的差異。在進行NIPAAm和AA的共聚合研究之前，我們先研究NIPAAm的均聚合研究，我們發現NIPAAm在scCO2中的反應速率比在MeOH中慢，但聚合度較高，在scCO2中所聚合的PNIPAAm分子量最高可達120萬，而在甲醇中所聚合的最高分子量只有30萬。凝膠滲透層析儀(gel permeation chromatography, GPC)不適合用來量測PNIPAAm的分子量，GPC所量測出的分子量會遠小於真實的分子量，並會隨分子量越高誤差會越大，可能因為PNIPAAm在四氫氟喃(THF)溶液中分子間或內氫鍵的作用力，在GPC高壓下會使PNIPAAm於溶液中團聚所致。MeOH中所聚合的低分子量的PNIPAAm在水溶液中，和水之間的氫鍵作用力可能大於scCO2中所聚合的PNIPAAm，以致於MeOH中所聚合的低分子量的PNIPAAm的較低溶解溫度(lower critical solution temperature, LCST)會略高於scCO2中所聚合的。而NIPAAm和AA在scCO2和甲醇中的共聚合反應，發現scCO2中所聚合的共聚物的產率和分子量都會低於甲醇中的，scCO2中的共聚合產率會隨NIPAAm/AA的進料莫爾比下降而下降。NIPAAm和AA在scCO2和MeOH中的共聚合反應都是屬於有恆比點(azeotropic composition)的共聚合反應，scCO2中所聚合的共聚物中AA的含量會少於甲醇中所聚合的，並且共聚物中AA的含量會隨反應壓力下降(2000~4000 psi)而增加。兩溶液中的共聚物的Tg會隨AA含量的增加先上升後下降，甲醇中的共聚物在酸性和鹼性溶液中於室溫下成膜，其Tg會高於在中性溶液中成膜的。在scCO2中所聚合的共聚物的LCST都會小於甲醇中所聚合的。最後我們在MeOH和scCO2中的NIPAAm的均聚合反應中添加多壁奈米碳管(multiwall carbon nanotube, MWCNT)，發現MWCNT會清除自由基，提高均聚物PNIPAAm的分子量。在scCO2中，自由基的清除率高達約90% (四小時的反應時間，分子量從37萬提高到116萬 g/mol)，在MeOH中只有51% (四小時的反應時間，分子量從28萬提高到40萬 g/mol)，可能由於scCO2的高擴散能力，使自由基與MWCNT的碰撞機會提高所致。 In this study, the free-radical copolymerizations of N-isopropylacrylamide (NIPAAm) and acrylic acid (AA) in supercritical carbon dioxide (scCO2) utilizing azobisisobutyronitrile (AIBN) as a free radical initiator were investigated. The copolymerizations of NIPAAm and AA in scCO2 were also compared with those in methanol (MeOH). In the absence of AA, the polymerization rate of NIPAAm in scCO2 was slower than that in MeOH whereas the degree of polymerization in scCO2 was higher than that in MeOH. The highest molecular weight of PNIPAAm polymerized in scCO2 was 1.2 million g/mol, but that of PNIPAAm polymerized in MeOH was only 0.3 million g/mol. Gel permeation chromatography (GPC) was not suitable for the characterization of high molecular weight PNIPAAm. PNIPAAm of lower molecular weights (MWs) gave more significant hydrogen-bonding interactions with water and thus exhibited higher LCST (lower critical solution temperature) for PNIPAAm polymerized in MeOH. Yields and MWs of the copolymers polymerized in scCO2 were lower than that polymerized in MeOH, with the yields decreasing with increasing feed of AA. The mole fraction of AA in the copolymer polymerized in scCO2 was lower than that polymerized in MeOH, and the mole fraction of AA in the copolymer polymerized in scCO2 was increasing with decreasing pressure of scCO2 in the range of 2000 to 4000 psi. The glass transition temperature (Tg) of the copolymer was increasing with increasing content of AA in the NIPAAm-rich copolymers but decreasing with increasing content of AA in the AA-rich copolymers. The Tg of the copolymer film formed in alkaline or acidic aqueous solution was higher than that in neutral aqueous solution. Finally, multiwalled carbon nanotubes (CNT) was found to retard polymerizations of NIPAAm but bring about an increase in MWs of PNIPAAm in both scCO2 and MeOH, with the effects of CNT more significant in scCO2 than in MeOH. This can be associated with the loss of radicals due to being scavenged by CNT in the polymerizations of NIPAAm.
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