TW201408761A - 兼具超疏水及超親油功能的複合物 - Google Patents
兼具超疏水及超親油功能的複合物 Download PDFInfo
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Abstract
一種兼具超疏水及超親油功能的複合物,包含有一多孔性材料以及一表層。該多孔性材料包含一骨架以及複數個形成於該骨架內並相連通的連通孔,該骨架包括複數個彼此相接的骨幹;該表層披覆於該骨幹表面,並包含一固著物以及複數個藉由該固著物附著於該骨幹表面的石墨烯片,其中,該石墨烯片順應該骨幹而形成一粗糙表面。據此,該複合物不僅具有超親油性,還具有超疏水性,而可用於水中油污或有機污染物的吸收,並具有可重覆使用的優點。
Description
本發明為有關一種複合物,尤指一種兼具超疏水性及超親油性的複合物。
石油及石化工業的發展,雖然供給人們生活上所需的能源及產品,但是相對的,也造成大自然環境許多的污染。
例如海洋石油開採的洩漏、海上石油運輸的事故溢油以及工業廢油的惡意排放等,皆對大自然的環境及生物造成重大的傷害,而對於此種污染的處理,一般為使用吸附劑與除油劑,再配合生物製劑加速石油的降解。不過,由於此種方式不僅過程複雜且成本高,因此,於美國專利公開第20120031846號中,提出一種以改質黏土收集油脂的方法,為將改質黏土與油脂混合,使該油脂被吸收於該改質黏土中。此種改質黏土為以親油性高分子化合物插層層狀矽酸鹽黏土、雲母或滑石,使黏土的層間距離增加,而提高對原油的吸收能力並降低油脂收集的成本。
然而,上述的改質黏土,用於收集油脂時,不僅回收不易,無法重覆使用,且其改質黏土在初次使用的吸收重量比(原油/改質黏土)僅約20,因此仍有改善的空間。
本發明的主要目的,在於解決習知使用改質黏土收集油脂時,具有回收不易、無法重覆使用以及吸收重量比不佳的問題。
為達上述目的,本發明提供一種兼具超疏水及超親油功能的複合物,包含有一多孔性材料以及一表層。該多孔性材料包含一骨架以及複數個形成於該骨架內並相連通的連通孔,該骨架包括複數個彼此相接且以該連通孔相隔的骨幹;該表層披覆於該骨幹表面,並包含一固著物以及複數個藉由該固著物附著於該骨幹表面的石墨烯片。
其中,該石墨烯片順應該骨幹而形成一粗糙表面。
如此一來,本發明藉由於該多孔性材料的骨幹上,包覆該表層,令該複合物至少具有下列優點:
1.該複合物不僅具有超親油性,還具有超疏水性,可用於水中油污或有機污染物的吸收。
2.該複合物於吸收油污或有機污染物後,可利用扭擠或蒸餾的方式將油污或有機污染物排出而能重覆使用。
3.該複合物所吸收的油污或有機污染物,相對該複合物,具有一大於50的重量比值(油污/複合物,或是有機污染物/複合物)。
有關本發明的詳細說明及技術內容,現就配合圖式說明如下:
請搭配參閱『圖1』及『圖2A』至『圖2C』所示,『圖1』為本發明一實施例的外觀立體示意圖,『圖2A』至『圖2C』分別為本發明一實施例中,多孔性材料之掃描式電子顯微鏡照片、石墨烯片包覆多孔性材料之掃描式電子顯微鏡照片以及固著物黏著石墨烯片之掃描式電子顯微鏡照片,本發明為一種兼具超疏水及超親油功能的複合物10,包含有一多孔性材料11以及一表層12。該多孔性材料11可為一具有多孔性結構(porous structure)之物質,其可為高分子、金屬或陶瓷,於本發明中,該多孔性材料11較佳地由高分子材質製成且呈現一海綿狀結構,例如一海綿,該多孔性材料11的材質可為木纖維素(lignocellulose)、纖維素(cellulose)、發泡塑料聚合物、聚醚(polyeether)、聚乙烯醇、三聚氰胺(melamine)、聚氨酯(polyurethane)和聚酯(polyester)。在此,該多孔性材料11包含一骨架111以及複數個形成於該骨架111內並相連通的連通孔112,該骨架111包括複數個彼此連接且以該連通孔112相隔的骨幹113,該連通孔112在此具有介於50微米至200微米的孔徑,但不以此為限制。
該表層12則披覆於該骨幹113表面,且該表層12包含一固著物及複數石墨烯片121(graphene sheet),該固著物黏著該石墨烯片121於該骨幹113的表面,而該石墨烯片121則順應該骨幹113而形成一粗糙表面122,在此實施例中,該石墨烯片121的厚度為介於0.5至5奈米之間,且該石墨烯片121相對該多孔性材料11,具有一介於5%至10%的重量比值,在此以該重量比值為7.3%為一較佳實施例,該粗糙表面122在此形成類荷葉狀(lotus leaf),而擁有疏水的特性。請參閱『圖3』所示,為本發明一實施例石墨烯片對多孔性材料的重量比值對複合物與水形成的接觸角關係示意圖,要補充說明的是,當該重量比值小於5%時,該複合物10與水接觸時,將快速的吸收水,而隨著重量比值逐漸增加,與水的接觸角由140°逐漸上升至160°,顯示該複合物10的疏水性也隨之提升,並於該重量比值達到7.3%時,該複合物10與水的接觸角約可達到160°至170°之間。
該複合物10於製造上,首先取得一塊該多孔性材料11,將該多孔性材料11依序置入丙酮溶液及蒸餾水中,並分別經過超音波震洗,再將該多孔性材料11取出置入一真空腔體中透過100°C且數小時的高溫烘烤,直至完全移除該多孔性材料11中的丙酮與蒸餾水,如『圖2A』所示;接著,將該多孔性材料11泡入含有複數石墨烯碎片的乙醇中,單一個石墨烯碎片的寬度大約介於0.15至10微米之間,厚度約為0.5至5奈米之間,關於該石墨烯碎片可由參考文獻「D. D. Nguyen, N. H. Tai, Y. L. Chueh, S. Y. Chen, Y. J. Chen, W.S. Kuo, T. W. Chou, C. S. Hsu and L. J. Chen, Nanotechnology,2011, 22, 295606.」中所述的石墨烯剝離而得,但不以此方式為限制取得石墨烯碎片的方法。
接續,將附著有該石墨烯碎片的該多孔性材料11,置入該真空腔體經過2小時且100°C的高溫烘烤後,該石墨烯碎片藉由凡得瓦力的作用包覆該多孔性材料11的骨幹113表面,形成該石墨烯片121及該粗糙表面122,如『圖2B』所示。最後,為了加強該石墨烯片121與該多孔性材料11的骨幹113之間的附著,將該石墨烯片121連同該多孔性材料11的骨架111泡入一含有聚二甲基矽氧烷(PDMS)的二甲苯(xylene)溶液中,之後再取出並以120°C烘烤數小時,使該聚二甲基矽氧烷滲入該石墨烯片121與該骨幹113之間的空隙,而形成該固著物將該石墨烯片121黏牢於該骨幹113上,如『圖2C』所示,不過該固著物並不限定為由聚二甲基矽氧烷製成,實際上,該固著物可選用任何兼具親油性與附著能力之高分子材料,例如聚二甲基矽氧烷(PDMS)、聚四氟乙烯(teflon)、陽離子交換樹脂(sulfonated polystyrene)、氟烯磺酸聚合物(nafion)、聚苯乙烯(polystyrene)、聚乙烯(polyethylene,PE)、聚丙烯(polypropylene,PP)、乙烯丙烯氟化物(fluorinated ethylene propylene,FEP)、聚異丁稀(polyisobutylene,PIB)、聚甲基丙烯酸叔丁酯(poly t-butyl methacrylate,PtBMA)等材料
請參閱『圖4A』至『圖4C』所示,『圖4A』為本發明一實施例將水及機油滴於複合物表面的示意圖,『圖4B』為本發明一實施例複合物與水的接觸角示意圖,『圖4C』為本發明一實施例複合物與機油的接觸角示意圖,如圖所示,在本實施例中,將水20及機油30分別滴在該複合物10的表面上,於『圖4A』中,顯示出水20於該複合物10的表面上,形成球狀,並未滲入該複合物10中,而機油30則被該複合物10吸收,滲入該複合物10中,進一步的,於『圖4B』中,顯示該複合物10的表面與水20形成一約為162°的接觸角α,於『圖4C』中,顯示該複合物10的表面與機油30形成一為0°的接觸角,而證明該複合物10具有良好的疏水性及親油性,再者,一般機油與聚二甲基矽氧烷之間的接觸角約為19°,而與石墨烯之間的接觸角約為15°,於本實施例中,該表層12包含該石墨烯片121以及該固著物,而該固著物可選擇使用以聚二甲基矽氧烷製成,亦可說明該複合物10具有良好的親油性。另外,於本發明中,該多孔性材料11之孔隙率(Porosity)應為一較佳之範圍區間,倘高於此區間,該連通孔112的孔徑將過小,不利油污或有機污染物之吸收;反之,若低於此區間,該連通孔112的孔徑將過大,而無法提供足夠之毛細孔力,同樣不利於油污或有機污染物之吸收。
請參閱『圖5A』至『圖5C』所示,『圖5A』為本發明一實施例複合物對具不同pH值的水溶液形成的接觸角關係示意圖,『圖5B』為本發明一實施例複合物對油污循環吸收的吸收能力示意圖,『圖5C』為本發明一實施例複合物對有機污染物循環吸收的吸收能力示意圖,於『圖5A』中,為具有pH值為2至14之間的不同水溶液,分別與該複合物10接觸,並各形成介於150°至165°之間的接觸角,說明該複合物10的疏水性,可適用於各種受污染而具有不同pH值的水質環境,而使得該複合物10在使用環境上,具有廣泛的應用性。
於『圖5B』中,為將該複合物10與各種油污接觸進行吸收,該油污例如可為用過的幫浦油(used pump oil)、幫浦油(pump oil)、大豆油(soybean oil)以及機油(motor oil),於該複合物10第1次接觸該油污並吸收飽和後,使用扭擠的方式去除該複合物10所吸收的該油污,再與該油污進行第2次吸收、第2次去除,接著第3次吸收、第3次去除,以此環循。
為了解本發明兼具超疏水及超親油功能的複合物之吸收能力,係定義一吸收能力值κ,吸收能力值κ為該複合物10的飽和吸收重量Ws減去吸收前重量Wi後,再除以吸收前重量Wi,即κ=(Ws-Wi)/Wi,且記錄每一次吸收的吸收能力值κ,從『圖5B』中得知,該複合物10於第1次與該油污進行接觸吸收時,其吸收能力值κ可達80以上,而於第2次、第3次與該油污進行接觸吸收,雖其吸收能力值κ仍約有20以上,因此說明該複合物10對於油污的吸收具有環循使用的潛力。
於『圖5C』中,為將該複合物10與各種有機污染物接觸以進行多次的吸收與排出,其中,當該複合物10係用於吸收有機汙染物,則較佳地採用蒸餾法(distillation)去除已吸收的有機汙染物,由於其通常可於低於150℃之溫度蒸發,故較佳地採用蒸餾法去除。如圖所示,該有機污染物例如可為甲醇(methanol)、乙醇(ethanol)、丙酮(acetone)、己烷(hexane)、二甲基甲醯胺(DMF)、三氯甲烷(chloroform)等,同樣的,記錄每一次吸收的吸收能力值κ,從『圖5C』中得知,該複合物10於第1次與該有機污染物進行接觸吸收時,依各種有機污染物的不同,吸收能力值κ介於54至165之間,且於第2次、第3次與該有機污染物進行接觸吸收,其吸收能力值κ仍維持前次水準,因此說明該複合物10對於有機污染物的吸收,具有環循使用的效果。
另外,於上述實施例中,係以該複合物10吸收如甲醇(methanol)、乙醇(ethanol)、丙酮(acetone)、己烷(hexane)、二甲基甲醯胺(DMF)、三氯甲烷(chloroform)等之有機污染物,以及如使用過之幫浦油(used pump oil)、幫浦油(pump oil)、大豆油(soybean oil)、機油(motor oil)等之油污做為舉例,然本發明之用途並不限於此,其更可用於吸收如辛烷(octane)、癸烷(decane)、十二烷(dodecane) 、蔬菜油(vegetable oil)、氣油(gasoline)、石油醚(petroleum ether)、柴油(diesel oil)、變壓器油(transformer oil)、潤滑油(lubricating oil)等等。
綜上所述,由於本發明藉由於該多孔性材料的骨幹上,包覆該表層,令該複合物不僅具有超親油性,還具有超疏水性,可用於水中油污或有機污染物的吸收,其中,該複合物在初次使用時,對油污的吸收能力值κ即可大於80,對有機污染物的吸收能力值κ介於54至165之間。再者,該複合物於吸收油污或有機污染物後,可利用扭擠或蒸餾的方式將油污或有機污染物排出而能重覆使用。最後,該複合物還具有製程簡單,成本便宜,容易量產等優點,因此本發明極具進步性及符合申請發明專利的要件,爰依法提出申請,祈 鈞局早日賜准專利,實感德便。
以上已將本發明做一詳細說明,惟以上所述者,僅爲本發明的一較佳實施例而已,當不能限定本發明實施的範圍。即凡依本發明申請範圍所作的均等變化與修飾等,皆應仍屬本發明的專利涵蓋範圍內。
10...複合物
11...多孔性材料
111...骨架
112...連通孔
113...骨幹
12...表層
121...石墨烯片
122...粗糙表面
20...水
30...機油
α...接觸角
κ...吸收能力值
圖1,為本發明一實施例的外觀立體示意圖。
圖2A,為本發明一實施例中,多孔性材料之掃描式電子顯微鏡照片。
圖2B,為本發明一實施例中,石墨烯片包覆多孔性材料之掃描式電子顯微鏡照片。
圖2C,為本發明一實施例中,固著物黏著石墨烯片之掃描式電子顯微鏡照片。
圖3,為本發明一實施例石墨烯片對多孔性材料的重量比值對複合物與水形成的接觸角關係示意圖。
圖4A,為本發明一實施例將水及機油滴於複合物表面的示意圖。
圖4B,為本發明一實施例複合物與水的接觸角示意圖。
圖4C,為本發明一實施例複合物與機油的接觸角示意圖。
圖5A,為本發明一實施例複合物對具不同pH值的水溶液形成的接觸角關係示意圖。
圖5B,為本發明一實施例複合物對油污循環吸收的吸收能力示意圖。
圖5C,為本發明一實施例複合物對有機污染物循環吸收的吸收能力示意圖。
112...連通孔
12...表層
122...粗糙表面
Claims (8)
- 一種兼具超疏水及超親油功能的複合物,包含有:
一多孔性材料,該多孔性材料包含一骨架以及複數個形成於該骨架內並相連通的連通孔,該骨架包括複數個彼此相接且以該連通孔相隔的骨幹;以及
一披覆於該骨幹表面的表層,該表層包含一固著物以及複數個藉由該固著物附著於該骨幹表面的石墨烯片;
其中,該石墨烯片順應該骨幹而形成一粗糙表面。 - 如申請專利範圍第1項所述的兼具超疏水及超親油功能的複合物,其中該複合物與水之間具有一介於150°至170°之間的接觸角。
- 如申請專利範圍第1項所述的兼具超疏水及超親油功能的複合物,其中該複合物與油之間具有一介於0°至10°的接觸角。
- 如申請專利範圍第1項所述的兼具超疏水及超親油功能的複合物,其中該固著物為擇自由聚二甲基矽氧烷、聚四氟乙烯、陽離子交換樹脂、氟烯磺酸聚合物、聚苯乙烯、聚乙烯、聚丙烯、乙烯丙烯氟化物、聚異丁稀與聚甲基丙烯酸叔丁酯所組成之群組。
- 如申請專利範圍第1項所述的兼具超疏水及超親油功能的複合物,其中該石墨烯片相對該多孔性材料具有一介於5%至10%的重量比值。
- 如申請專利範圍第1項所述的兼具超疏水及超親油功能的複合物,其中該連通孔具有一介於50微米至200微米的孔徑。
- 如申請專利範圍第1項所述的兼具超疏水及超親油功能的複合物,其中該多孔性材料的材質為擇自由木纖維素、纖維素、發泡塑料聚合物、聚醚、聚乙烯醇、三聚氰胺、聚氨酯與聚酯所組成之群組。
- 如申請專利範圍第1項所述的兼具超疏水及超親油功能的複合物,其中該多孔性材料呈現一海綿狀結構。
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