常壓電漿接枝聚N-異丙基丙烯醯胺於聚偏二氟乙烯薄膜之研究

Rapid Grafting of Poly(N-isopropylacrylamide) onto Poly(vinylidene fluoride) Membranes by Atmospheric Pressure Plasma Jet

王敬為(Chin-Wei Wang)

指導教授 ： 魏大欽

中原大學/工學院/化學工程研究所/碩士(2010年)

https://doi.org/10.6840/cycu201000581

摘要

本研究以常壓電漿對聚偏二氟乙烯同時進行表面活化與接枝的步驟，使膜材接枝上聚N-異丙基丙烯醯胺以製備溫敏性之材料，探討單體濃度、電漿操作參數和不同製程對於膜材溫敏性質之影響，利用接枝量(Grafting density)、全反射式傅立葉轉換紅外線光譜儀(FTIR-ATR)、掃描式電子顯微鏡(SEM)和化學分析電子儀分析儀器(ESCA)與變溫接觸角量測(Thermo contact angle)之結果進行分析。

研究發現利用常壓電漿製備PVDF-g-PNIPAAm的PNIPAAm接枝量太低導致無明顯之溫敏性變化。而先行利用常壓電漿製備PVDF-g-PEGMA後再利用常壓電漿製備PVDF-g-(PPEGMA/PNIPAAm)除了可以提升PNIPAAm於改質膜上之接枝量外，經由變溫接觸角量測結果發現在電漿處理時間為20s時就有明顯之溫敏性質(當溫度為20℃時接觸角為56.1°而當溫度為40℃時接觸角為84.1°)。除此之外經由ESCA之N/C和O/C分析20s時之單體結構保有度，發現在此電漿處理時間下由於單體結構保有度相較於其他電漿處理時間而言較佳，因此溫敏性質較為明顯，此外經由變溫接觸角量測發現PNIPAAm之LCST約為26℃。另外將兩種單體(NIPAAm和PEGMA)於IPA中均勻混合後利用常壓電漿製備PVDF-g-P(NIPAAm-co-PEGMA)一樣有溫敏性之變化，而藉由添加不同比例之PEGMA發現到PNIPAAm之LCST有往高溫方向移動之趨勢。這與文獻所提到藉由適當分子設計可改變PNIPAAm之LCST結果相符。

本研究所開發的常壓電漿接枝方法可以快速、乾淨、簡便的製備溫敏性之材料，除此之外也可運用在其他單體的接枝方面，是一種極有潛力的技術。

關鍵字

甲基丙烯酸聚乙二醇酯 ； 聚N-異丙基丙烯醯胺 ； LCST ； 聚偏二氟乙烯 ； 常壓電漿

並列摘要

The objective of this research is using the atmospheric pressure plasma jet (APPJ) to graft poly(N-isopropylacrylamide) (PNIPAAm) onto poly(vinylidene fluoride) (PVDF) membranes. The chemical structure, surface morphology and thermo-responsive behavior of the surface-modified PVDF membranes are characterized by fourier transform infrared attenuated total reflectance (FTIR-ATR), electron spectroscopy for chemical analysis (ESCA), scanning electron microscopy (SEM) and contact angle.

The experimental results show that the grafting density is low and substrate is slightly etched in the grafting of PVDF-g-PNIPAAm membranes. With the addition of poly(ethylene glycol) methactylate (PEGMA), the grafting density of PNIPAAm is significantly improved and thermo-responsive characteristics are shown in the resulting membranes. The remarkable change in water contact angle (56.1° at 20oC and 84.1° at 40oC) can be seen on PVDF-g-(PPEGMA/PNIPAAm) when the APPJ grafting time is just 20s. Furthermore, the ESCA results show that the molecular structure at the grafting time 20s is better than other grafting times. Therefore, the resulting membranes also shows the highest thermo-sensitivity as seen in the differences of contact angle. Besides, the lower critical solution temperature (LCST) of the PVDF-g-(PPEGMA/PNIPAAm) is about 26 oC.

Another thermo-responsive membranes can also be observed on PVDF-g-P(NIPAAm-co-PEGMA). The FTIR results show that the PNIPAAm amount in PVDF-g-P(NIPAAm-co-PEGMA) is more than that of modified membranes. The thermo-sensitivity in the resulting membranes show significant difference when the PEGMA ratio in the copolymer is increased. Furthermore, the LCST of PVDF-g-P(NIPAAm-co-PEGMA) shifts to higher temperature if the PEGMA content in the membranes is increased. That is because the PNIPAAm has been randomly copolymerized with different ratio of hydrophilic monomers.

並列關鍵字

Atmospheric pressure plasma jet ； Lower critical solution temperature ； Poly(ethylene glycol) methactylate ； Poly(vinylidene fluoride) ； Poly(N-isopropylacrylamide)

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