- 學位論文
電漿改質PNIPAAm-g-PVDF熱響應薄膜特性研究
Study on the properties of plasma modified thermoresponsive PNIPAAm-g- PVDF membranes
摘要
本研究成功利用電漿誘導後接枝聚合的方式，在多孔性的聚偏氟乙烯 (PVDF) 基材膜上接枝熱響應性單體氮異丙基丙烯醯胺 (NIPAAm) ，並製備一系列不同接枝度之熱響應複合薄膜，探討接枝度對於熱響應特性之影響。由Fourier Transform Infrared Spectroscopy(FT-IR)及X-ray photoelectron spectroscopy(XPS)的元素分析可証實接枝反應成功進行，且PNIPAAm之C=O 及-NH官能基可被保留下來。研究中探討電漿功率、NIPAAm單體濃度以及後接枝聚合時間對於接枝度之影響，結果顯示，接枝度隨著單體濃度和接枝時間增加而上升。由掃描式電子顯微鏡 (SEM) 觀察到薄膜表面的覆蓋率隨著接枝度上升而增加，並由截面發現接枝高分子不僅接枝在表面，膜內孔洞也成功進行接枝反應。經由變溫對水接觸角(20/40℃)的量測以及純水透過測試 (20℃-50℃) 得知PNIPAAm-g-PVDF複合膜具備良好之熱響應特性；在低於lower critical solution temperature(LCST) (32℃) 時PNIPAAm呈現伸張狀態而較親水，高於 LCST時則呈現收縮狀態且較疏水；其純水透過量在高於LCST時會因為PNIPAAm分子鏈收縮使孔洞增大而有顯著的提升。隨著接枝度增加，PNIPAAm-g-PVDF之熱響應特性會有先上升後下降之特性，這是由於接枝度增加，PNIPAAm的伸張收縮情形越明顯，但接枝度過高會導致PNIPAAm的高分子鏈堵塞孔洞，而無法有效伸張或收縮；在藥物釋放上，其結果與純水透過測試相符，在PNIPAAm-g-PVDF複合膜(G.D.=10.1%)時具有最佳之熱響應特性；藉由正子湮滅壽命光譜（Positron annihilation lifetime Spectroscopy, PALS）的量測，可得知在溫度高於(LCST) 時，其自由體積會出現雙連續的分布，此結果可有效關聯到PNIPAAm分子鏈的收縮行為。
並列摘要
Poly(N-isopropylacrylamide) (PNIPAAm) was successfully grafted on the surface of poly(vinylidene fluoride) (PVDF) membranes by plasma induced post- graft polymerization method. A series of thermoresponsive grafting membranes with a wide range of grafting degree was prepared. The effect of the grafting degree on the thermal response characteristics was investigated. ATR-FTIR and XPS elemental analysis confirmed that the grafting reaction was successful and the functional group in PNIPAAm (C=O, -NH) was retained. The effect of plasma power, monomer concentration and grafting time on grafting degree was investigated. Results showed that the grafting degree increased with increasing the monomer concentration and grafting time. From SEM observation, the surface coverage of PNIPAAm was increased with the increase in grafting degree. Results of water contact angle measurement and pure water permeation test showed that PNIPAAm-g-PVDF had a good thermal responsibe.The PNIPAAm polymer chain was shrink and exhibited a hydrophobic character when the temperature was higher than LCST; lower than the LCST,it was stretched and showed a hydrophilic behavior. When the grafting degree increased, the thermal response of PNIPAAm chain first increased than decreased. The higher the grafting degree the stronger the response of PNIPAAm. However, the pores were plugged by the PNIPAAm chain when the grafting degree was too high and resulted in shrinking or stretching the PNIPAAm chain . In drug delivery, and the results match with water permeation test, the GD = 10.1%, have the best thermal response property. By using positron annihilation lifetime (PALS) analysis, the free volume in PNIPAAm-g-PVDF membrane showed a bimodel distribution when T>LCST. This result could be related to the shrinking behavior of the PNIPAAm polymer chain.
參考文獻
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