指導教授：邱文英臺灣大學：化學工程學研究所張芳慈Chang, Fang-TzuFang-TzuChang2014-11-252018-06-282014-11-252018-06-282014http://ntur.lib.ntu.edu.tw//handle/246246/261178本研究利用雙軸靜電紡絲技術製備芯鞘型溫感性導電複合纖維，內軸使用材 料為具可撓性之軟性鏈段高分子Poly(butyl acrylate-co-styrene) (PBS)，外軸則是溫度敏感可交聯性高分子Poly(NIPAAm-co-NMA) (PNN)與導電高分子PEDOT:PSS混摻製備而成。 將單體氮-羥甲基丙烯醯胺(NIPAAm)與可交聯性單體氮-異丙基丙烯醯胺(NMA)利用溶液聚合法可合成溫感性可熱交聯共聚物PNN；丙烯酸丁酯(Butyl acrylate)與苯乙烯(Styrene)藉由乳化聚合合成柔韌性共聚物PBS。在雙軸靜電紡絲製程中，內軸電紡溶液為PBS/chloroform，外軸電紡溶液則是使用兩種不同組成來分別進行雙軸靜電紡絲：第一部分為PNN、PEDOT:PSS/water，第二部分為PNN、PEDOT:PSS/water+DMSO。製備出的芯鞘型複合纖維可利用SEM與TEM觀察其形態變化，本研究也發現內軸電紡溶液黏度需高於1Pa‧s時，才可得到均勻且連續的芯鞘型纖維，此纖維的外徑約為250-350nm，其中內徑約佔150-200nm。 利用方法一收集而成的複合纖維膜加熱交聯後，需經由DMSO的 doping才可使PEDOT的導電提升，但也因此溶出了部分內軸材料PBS。此方法製得的複合纖維膜因PNN含量多，在溫度改變時，表面電阻的變化明顯，但在可撓性測試中，發現纖維經過來回的彎曲測試後會容易斷裂。為改善此現象，方法二使用的外軸溶劑改成以DMSO與水的共溶劑，在溶液混合時即產生doping作用，故可省略後續的doping製程，交聯後的芯鞘纖維因內軸具有柔韌性材料PBS，使其具可撓性而不會輕易斷裂，但在溫度敏感的導電性測試中，表面電阻的變化不明顯，且實驗溫度接近PBS的Tg，使得其溫感變化會受到PBS分子鏈運動的干擾。In this research, thermo-responsive and conductive composite fibers with sheath-Core structure were fabricated by co-axial electrospinning. The thermo-responsive and thermo-crosslinkable copolymer poly(NIPAAm-co-NMA) (PNN) and conductive PEDOT:PSS were mixed as the sheath material and the flexible copolymer poly(butylacrylate-co-styrene)(PBS) was prepared as the core. Thermo-responsive copolymer PNN which composed of N-isopropylacrylamide (NIPAAm) and N-methyloacrylamide were synthesized by solution polymerization. Flexible copolymer PBS which composed of butylacrylate and styrene were synthesized by emulsion polymerization.In this co-axial electrospinning process, the core solution was prepared by dissolving PBS in chloroform.Two kind of sheath solution was prepared for electrospinning process：(1) PNN/PEDOT:PSS in water、(2) PNN/PEDOT:PSS in water＋DMSO. The morphology of the composite fibers were observed by SEM and TEM. To fabricate optimum sheath-core fibers, the critical viscosity of the core solution should exceed 1Pa．s. The outer diameters of fibers were about 250-350nm and the inner diameters were about 150-200nm. In the first method, The fiber mat should be doped by DMSO after thermal curing to enhence conductive property, but it was found out that the core material PBS was partially dissolved. In the thermo-responsive conductive property measurement, surface resistivity of fiber mat would change with temperature.When the temperature increased from 25℃ to 50℃, the surface resistivity of this fiber mat decreased gradually owing to thermo-responsivity. In the flexibility test, after bending this fiber mat several times, it would fracture easily owing to leakage of PBS. To solve this problem, we used the second method. By changing the solution, fiber mat wouldn’t be necessary to be doped in DMSO after thermal curing. The flexibility of sheath-core composite fiber mat was improved because of the higher content of PBS. In the thermo-responsive conductive property measurement,because the working temperature was near the Tg of PBS, the surface resistivity was disturbed by motion of PBS chains.目錄 口試委員會審定書 # 誌謝 i 中文摘要 ii ABSTRACT iii 目錄 v 圖目錄 ix 表目錄 xi 第一章 緒論 1 1.1前言 1 1.2研究目的 1 第二章 文獻回顧 2 2.1導電高分子PEDOT:PSS 2 2.1.1共軛導電高分子 2 2.1.2 PEDOT:PSS簡介 3 2.1.3 PEDOT:PSS應用 4 2.2溫度敏感型高分子Poly(NIPAAm) 6 2.2.1環境敏感型高分子 6 2.2.2溫度敏感型高分子 7 2.3靜電紡絲技術 11 2.3.1靜電紡絲發展 11 2.3.2靜電紡絲原理與裝置 12 2.3.3靜電紡絲參數 14 2.3.4雙軸電紡絲技術 19 第三章 實驗方法 22 3.1實驗藥品 22 3.2實驗儀器 26 3.3實驗步驟 28 3.3.1實驗流程圖 28 3.3.2合成Poly(NIPAAm-co-NMA)與Poly(BA-co-Styrene) 29 3.3.3利用靜電紡絲技術製備複合奈米纖維 31 3.4材料分析 33 3.4.1分子量測定 33 3.4.2玻璃轉移溫度(Glass transition temperature, Tg)之測定 33 3.4.3低臨界溶液溫度（LCST）之測定 34 3.5複合纖維形態觀察 34 3.6複合纖維性質分析 35 3.6.1膨潤率量測(Swelling ratio) 35 3.6.2孔隙率之測定 36 3.6.3表面電阻隨溫度變化之測定 37 3.6.4可撓性測試 38 第四章 結果與討論 39 4.1材料分析 39 4.1.1分子量測定 39 4.1.2 PBS玻璃轉移溫度(Glass transition temperature, Tg) 之測定 39 4.1.3 PDPNN低臨界溶液溫度（LCST）之測定 40 4.2影響複合纖維形態之因素 40 4.2.1電紡溶液黏度與表面張力 40 4.2.2電壓大小 43 4.2.3不同BA與Styrene之比例 44 4.3影響複合纖維表面電阻之因素 44 4.3.1交聯時間 44 4.3.2不同BA與Styrene之比例 45 4.3.3改善內軸PBS溶出問題 46 4.3.4孔隙率(方法二) 47 4.4膨潤率(swelling ratio) 48 4.5表面電阻隨溫度之變化 49 4.6複合纖維可撓性測試 50 第五章 結論 70 參考文獻 724303410 bytesapplication/pdf論文公開時間：2019/07/29論文使用權限：同意有償授權(權利金給回饋學校)雙軸靜電紡絲溫度敏感導電纖維可撓性thesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/261178/1/ntu-103-R01524006-1.pdf