靜電紡絲製備醚型聚胺酯/改質奈米碳管複合材料及性質鑑定

Preparation of Ether-typed Polyurthane/Modified Carbon Nanotube Composites Using Electrospinning Method and Property Studies

潘彥曲(Yan-Chiu Pan)

指導教授 ： 王賢達

國立臺北科技大學/工程學院/有機高分子研究所/碩士(2013年)

摘要

本研究以預聚合法將聚氧四亞基二醇(PTMO)和4,4’-二苯甲烷二異氰酸鹽(MDI)先形成預聚物，再加入1,4-丁二醇(1,4-BD)鏈長劑合成聚胺酯(PU)；改質PU則在鏈延長過程中加入2-胺基丙二醇(N-BOC-serinol)合成改質PU，再將其活化去除N-BOC保護基形成活化PU。市售奈米碳管經570℃鍛燒、氫氟酸、硝酸振盪後可得純化奈米碳管，接著以H2SO4/ HNO3進行酸化處得到酸化奈米碳管，最後加入亞硫醯氯反應形成醯氯化多壁奈米碳管。將活化PU與醯氯化多壁奈米碳管混和，並以靜電紡絲方法將其噴絲後再加熱使之形成具化學鍵結之聚胺酯/多壁奈米碳管複合材料(MWNTs/PU)。
經由FTIR、NMR鑑定其結構說明成功將奈米碳管接枝於改質PU中。SEM可觀察到纖維結構，其纖維平均直徑約在400nm；TEM則可發現奈米碳管被包覆在PU中，且大部分碳管會沿纖維方向排列。TGA及DMA熱分析數據顯示，當碳管添加的比例提高，則5%熱重損失溫度(Td)及玻璃轉移溫度(Tg)，分別由純PU的290℃及-34℃最高上升至322℃及-23℃。表面電阻方面，則隨碳管添加量增加下降，最低可降至5.4×109。拉伸測試結果顯示拉伸強度及楊氏模數會隨奈米碳管增加，且較純PU分別提高168%及946%；斷裂延伸率則由336%下降至195%。
全血液凝固動力測試數據顯示MWNTs/PU之吸光值較改質PU提升許多，表示加入碳管會使全血在纖維膜上不易凝固，增加其抗凝血性。而由MTT結果可說明我們的纖維膜不具毒性。

關鍵字

聚胺酯 ； 靜電紡絲 ； 奈米碳管 ； 複合材料

並列摘要

In this study, polyurethane(PU) was prepared using pre-polymer method with poly(tetramethylene oxide)(PTMO,MW1000) and 4,4-(diphenylmethane diissocyanate)(MDI) as starting materials and 1,4-butanediol as the chain-extender.
The modified PU was synthesized by adding N-BOC-serinol, during the chain extension process, and the product was de-protected the BOC groups of the incorporated N-BOC-serinol units. The pristine multi-walled carbon nanotubes (MWNTs) were air-oxidized at 570℃ to remove carbonaceous particles , sonificated with HF and HNO3 at room temperature to remove metal catalysts , and oxidized with
H2SO4/ HNO3( 3:1 by volume) in order to obtain the acidified-MWNTs(AMWNTs).
The MWNTs possessing COCl functional groups(ClMWNTs) were prepared by refluxing AMWNTs with SOCl2. The modified PU, ClMWNTs, and 4-dimethylaminopyridine (DMAP) were mixed and electrospun into web. The web was then heated in vacuum at 70℃ for 24h in order to get the chemically bonded composite.
PU and MWNTs/PU were characterized by 1H NMR and FTIR which demonstrated that ClMWNTs bonded to the modified PU. The structure of the web was investigated by SEM, and the average fiber diameter was about 400 nm. The TEM images showed most of the MWNTs inside the composite oriented along the axis of the nanofibers. The 5% weight loss temperature(Td) and the glass transition temperature measured by TGA and DMA, separately, increased with increasing MWNTs content of the composite. The surface electric resistivity reduced by increasing MWNTs content of the composite. The mechanical property data showed that the incorporation of MWNTs into composite would caus the increase in the ultimate tensile strength and the Young’s modulus, and result in the decrease of the elongation at break of the material.
Biocompatibilities were measured by the whole blood clotting tests and the cell viability tests (MTT tests). The results showed that the anticoagulation ability of MWNTs/PU was better than those of PU and modified PU, and with the more MWNTs inside the composite ,the less is the blood aggregation. The MTT tests indicated that PU, the modified PU and the MWNTs/PU composite were non-toxic to cells.

並列關鍵字

Polyurethane ； Carbon Nanotube ； Composite ； Electrospinning

參考文獻

[9]魏向辰，導電高分子與多層奈米碳管複合材料之研究，國立中央大學化學

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