TWI568781B - Sulfonated polymer/graphene nano-composite material and its preparation method and application - Google Patents
Sulfonated polymer/graphene nano-composite material and its preparation method and application Download PDFInfo
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本發明涉及石墨烯複合材料，特別是涉及一種磺化高分子/石墨烯奈米複合材料及其製備方法和應用。 The invention relates to a graphene composite material, in particular to a sulfonated polymer/graphene nano composite material and a preparation method and application thereof.
氧化銦錫(ITO)透明導電薄膜在太陽能電池、觸控式螢幕、平板顯示器等電子器件中廣泛應用，但製備氧化銦錫(ITO)透明電極的原材料銦是稀有貴金屬，且氧化銦錫(ITO)是無機氧化物薄膜，呈脆性，限制了其在柔性觸控屏中的應用。 Indium tin oxide (ITO) transparent conductive film is widely used in electronic devices such as solar cells, touch screens, flat panel displays, etc., but the raw material for preparing indium tin oxide (ITO) transparent electrode is rare precious metal, and indium tin oxide (ITO) It is an inorganic oxide film that is brittle, which limits its application in flexible touch screens.
自2004年英國曼徹斯特大學研究人員首次製備出單原子層石墨烯後，石墨烯展現出的優異電學性能在全世界已經掀起研究熱潮。石墨烯是碳原子形成的六角蜂巢晶格平面空間內排列組成的單原子層兩維材料，又稱為單原子層石墨，其獨特的結構決定了它既有高韌性，又有高剛性，化學穩定性好，光學和電學性能優異。單原子層石墨烯的可見光吸收率僅為2.3%，理論面電阻20Ω-1。石墨烯優異的光學和電學性能，高柔韌性和豐富的原材料，使其成為氧化銦錫(ITO)理想替代材料。當使用石墨烯來製備透明導電薄膜時，需要將石墨烯與高分子材料混合。然而，石墨烯分散于高分子中時往往會產生聚集的現象，造成所添加的石墨烯比例都很 低。 Since the first preparation of monoatomic graphene by researchers at the University of Manchester in the United Kingdom in 2004, the excellent electrical properties exhibited by graphene have set off a research boom around the world. Graphene is a monoatomic layered two-dimensional material composed of hexagonal honeycomb lattice planes formed by carbon atoms. It is also called monoatomic layer graphite. Its unique structure determines its high toughness and high rigidity. Good stability, excellent optical and electrical properties. The visible light absorption of monoatomic layer graphene is only 2.3%, and the theoretical surface resistance is 20 Ω -1 . Graphene's excellent optical and electrical properties, high flexibility and abundant raw materials make it an ideal replacement for indium tin oxide (ITO). When graphene is used to prepare a transparent conductive film, it is necessary to mix graphene with a polymer material. However, when graphene is dispersed in a polymer, aggregation tends to occur, resulting in a low proportion of graphene added.
基於此，有必要提供一種石墨烯含量較高的磺化高分子/石墨烯奈米複合材料。 Based on this, it is necessary to provide a sulfonated polymer/graphene nano composite with a high graphene content.
一種磺化高分子/石墨烯奈米複合材料，包括石墨烯和均勻分散在所述石墨烯層間的磺化高分子，所述石墨烯構成一導電網路。 A sulfonated polymer/graphene nano composite comprising graphene and a sulfonated polymer uniformly dispersed between the graphene layers, the graphene forming a conductive network.
一種磺化高分子/石墨烯奈米複合材料，包括石墨烯和均勻分散在所述石墨烯層間的磺化高分子，所述石墨烯構成一導電網路。 A sulfonated polymer/graphene nano composite comprising graphene and a sulfonated polymer uniformly dispersed between the graphene layers, the graphene forming a conductive network.
在其中一個事實例中，所述磺化高分子為帶有磺酸根鏈段的高分子。 In one of the examples, the sulfonated polymer is a polymer having a sulfonate segment.
在其中一個實施例中，所述磺化高分子選自磺化聚醯亞胺(Sulfonated polyimide)、磺化聚二乙炔(sulfonated polydiacetylene)及磺化聚(乙烯醇)(sulfonated poly(vinyl alcohol))中的一種。 In one embodiment, the sulfonated polymer is selected from the group consisting of a sulfonated polysulfide, a sulfonated polydiacetylene, and a sulfonated poly(vinyl alcohol). One of them.
在其中一個實施例中，所述石墨烯添加於所述磺化高分子/石墨烯奈米複合材料的重量百分比為0.1%~1%。 In one embodiment, the graphene is added to the sulfonated polymer/graphene nano composite in a weight percentage of 0.1% to 1%.
一種磺化高分子/石墨烯奈米複合材料的製備方法，包括如下步驟：將氧化石墨烯與磺化高分子在溶劑中混合得到混合溶液；及往所述混合溶液中加入還原劑進行還原反應得到磺化高分子/石墨烯奈米複合材料，所述磺化高分子/石墨烯奈米複合材料包括石墨烯和均勻分散在所述石石墨烯層間的磺化高分子。 A method for preparing a sulfonated polymer/graphene nano composite material, comprising the steps of: mixing graphene oxide with a sulfonated polymer in a solvent to obtain a mixed solution; and adding a reducing agent to the mixed solution for reduction reaction A sulfonated polymer/graphene nano composite material is obtained, the sulfonated polymer/graphene nano composite material comprising graphene and a sulfonated polymer uniformly dispersed between the stone graphene layers.
在其中一個實施例中，所述磺化高分子為有磺酸根鏈段的高分子。 In one embodiment, the sulfonated polymer is a polymer having a sulfonate segment.
在其中一個實施例中，所述磺化高分子選自磺化聚醯亞胺(Sulfonated polyimide)、磺化聚二乙炔(sulfonated polydiacetylene)、磺化聚(乙烯醇)(sulfonated poly(vinyl alcohol))中的一種。 In one embodiment, the sulfonated polymer is selected from the group consisting of a sulfonated polysulfide polycondensate, a sulfonated polydiacetylene, a sulfonated poly(vinyl alcohol). One of them.
在其中一個實施例中，所述石墨烯在所述磺化高分子/石墨烯奈米複合材料的重量百分比為0.1%~1%。 In one embodiment, the weight percentage of the graphene in the sulfonated polymer/graphene nano composite is 0.1% to 1%.
在其中一個實施例中，所述溶劑選自去離子水、二甲基亞碸、二甲基甲醯胺、N-甲基吡咯烷酮及乙醇中的一種。 In one embodiment, the solvent is selected from the group consisting of deionized water, dimethyl hydrazine, dimethylformamide, N-methylpyrrolidone, and ethanol.
在其中一個實施例中，所述氧化石墨烯添加於所述混合溶液中的濃度為1mg/ml。 In one embodiment, the graphene oxide is added to the mixed solution at a concentration of 1 mg/ml.
在其中一個實施例中，所述還原劑為聯胺。 In one embodiment, the reducing agent is a hydrazine.
在其中一個實施例中，往所述混合溶液中加入還原劑進行還原反應得到磺化高分子/石墨烯奈米複合材料的步驟為，按照氧化石墨烯與聯胺的比例為200mg/mL(50%濃度的聯胺)往所述混合溶液中加入聯胺，在25℃的溫度加入攪拌1分鐘，之後加熱到100℃下回流反應2小時，分離純化，進而得到磺化高分子/石墨烯奈米複合材料。 In one embodiment, the step of adding a reducing agent to the mixed solution to obtain a sulfonated polymer/graphene nano composite is as follows: the ratio of graphene oxide to hydrazine is 200 mg/mL (50 % concentration of hydrazine) Add hydrazine to the mixed solution, add and stir at 25 ° C for 1 minute, then heat to 100 ° C for 2 hours, separate and purify, and then obtain sulfonated polymer / graphene Rice composite.
所述磺化高分子/石墨烯奈米複合材料在觸控面板上的應用。 The application of the sulfonated polymer/graphene nano composite material on a touch panel.
當氧化石墨烯通過還原劑還原成石墨烯時，由於磺化高分子均勻穿插於氧化石墨烯的層間，因此在進行還原反應時，磺化高分子不會被石墨烯所排擠，因此能大幅增加石墨烯添加於高分子中的比例。 When graphene oxide is reduced to graphene by a reducing agent, since the sulfonated polymer is uniformly intercalated between the layers of the graphene oxide, the sulfonated polymer is not displaced by the graphene during the reduction reaction, and thus can be greatly increased. The ratio of graphene added to the polymer.
S101‧‧‧步驟 S101‧‧‧Steps
S102‧‧‧步驟 S102‧‧‧Steps
圖1為一實施方式的磺化高分子/石墨烯奈米複合材料的製備方法流程圖。 1 is a flow chart showing a method for preparing a sulfonated polymer/graphene nano composite according to an embodiment.
圖2為一實施方式的磺化高分子/石墨烯奈米複合材料的製備方法模擬圖。 2 is a simulation diagram of a method for preparing a sulfonated polymer/graphene nano composite according to an embodiment.
圖3為一實施例的磺化高分子/石墨烯奈米複合材料與純石墨烯的分散狀況對比照片。 3 is a comparative photograph of the dispersion state of a sulfonated polymer/graphene nano composite material and pure graphene according to an embodiment.
圖4為一實施例的磺化高分子/石墨烯奈米複合材料與純石墨烯的傅利葉紅外光譜圖。 4 is a Fourier infrared spectrum of a sulfonated polymer/graphene nanocomposite and pure graphene according to an embodiment.
圖5為實施例1的磺化高分子/石墨烯奈米複合材料的TEM照片。 5 is a TEM photograph of a sulfonated polymer/graphene nano composite of Example 1.
一實施方式的磺化高分子/石墨烯奈米複合材料，包括石墨烯和均勻分散在所述石墨烯層間的磺化高分子，所述石墨烯構成一導電網路。 The sulfonated polymer/graphene nano composite of one embodiment comprises graphene and a sulfonated polymer uniformly dispersed between the graphene layers, the graphene forming a conductive network.
優選的，磺化高分子為帶有磺酸根鏈段的高分子。 Preferably, the sulfonated polymer is a polymer having a sulfonate segment.
優選的，磺化高分子為選自磺化聚醯亞胺()、磺化聚二乙炔(
優選的，石墨烯在磺化高分子/石墨烯奈米複合材料的重量百分比為0.1%~1wt%。 Preferably, the weight percentage of graphene in the sulfonated polymer/graphene nano composite is 0.1% to 1% by weight.
請同時參閱圖1與圖2，上述磺化高分子/石墨烯奈米複合材料的製備方法，包括如下步驟： Please refer to FIG. 1 and FIG. 2 simultaneously, the preparation method of the above sulfonated polymer/graphene nano composite material, comprising the following steps:
步驟S101、將氧化石墨烯與磺化高分子在溶劑中混合得到混合溶液。 Step S101, mixing the graphene oxide and the sulfonated polymer in a solvent to obtain a mixed solution.
例如，可以將氧化石墨烯與磺化高分子分別加入不同容器內，並分別加入溶劑進行分散與溶解。溶解氧化石墨烯的溶劑可以選自去離子水、二甲基亞碸(DMSO)、二甲基甲醯胺(DMF)、N-甲基吡咯烷酮(NMP)及乙醇中的一種。溶解磺化高分子的溶劑可以選用二甲基亞碸(DMSO)或N-甲基吡咯烷酮(NMP)其中一種。優選的氧化石墨烯是採用超聲波震盪分散，再將均勻分散的氧化石墨烯逐步滴入磺化高分子內進行充分混和。氧化石墨烯在溶劑中的優選濃度為1mg/mL，磺化高分子的優選濃度為200mg/mL。氧化石墨烯添加於磺化高分子的比例可從0.1wt%到1wt%。在材料上，氧化石墨烯可以透過購買得到，或者是使用改良的Hummers法將石墨氧化後剝離製備得到。 For example, graphene oxide and sulfonated polymer can be separately added to different containers, and separately added to a solvent for dispersion and dissolution. The solvent for dissolving the graphene oxide may be selected from one of deionized water, dimethylarsine (DMSO), dimethylformamide (DMF), N-methylpyrrolidone (NMP), and ethanol. The solvent for dissolving the sulfonated polymer may be one selected from the group consisting of dimethyl hydrazine (DMSO) or N-methylpyrrolidone (NMP). The preferred graphene oxide is dispersed by ultrasonic vibration, and the uniformly dispersed graphene oxide is gradually dropped into the sulfonated polymer to be sufficiently mixed. The preferred concentration of graphene oxide in the solvent is 1 mg/mL, and the preferred concentration of the sulfonated polymer is 200 mg/mL. The proportion of the graphene oxide added to the sulfonated polymer may be from 0.1% by weight to 1% by weight. In terms of materials, graphene oxide can be obtained by purchase, or can be prepared by oxidizing and stripping graphite using a modified Hummers method.
石墨烯與高分子所面臨的最大問題在於相容性。現有文獻中記載的複合材料，其所混摻的石墨烯比例往往都很低，而在高比例下的石墨烯，又會造成聚集的現象產生，因此如何將高比例石墨烯均勻分散於高分子中，將是一大難題。 The biggest problem facing graphene and polymers is compatibility. The composite materials described in the existing literature tend to have a low proportion of graphene blended, and graphene at a high ratio causes aggregation phenomenon, so how to uniformly disperse a high proportion of graphene in the polymer. In, it will be a big problem.
請參閱圖3，純的石墨烯分散于水中且靜置1小時，即可看見石墨烯有沉降的產生。而當石墨烯分散於磺化聚亞醯胺溶液中，於相同的時間下，未發現石墨烯有沉降現象，這是因為石墨烯的表面存在著較多極性基團(例如-COOH、-OH等等)，這些極性基團能夠與磺酸根(-SO3H)產生氫鍵作用力。由圖4可知，當1wt%的石墨烯導入磺化聚亞醯胺時，其-OH基團會往高波數方向位移，因此可證明其氫鑒作用力的存在。而通過此作用力，還原後的石墨烯能均勻分散於高分子系統內。 Referring to Figure 3, pure graphene is dispersed in water and allowed to stand for 1 hour, and the formation of graphene is observed. When graphene was dispersed in the sulfonated polyamidamine solution, no graphene was found to settle at the same time because of the presence of more polar groups on the surface of graphene (eg, -COOH, -OH). Etc.) These polar groups are capable of generating hydrogen bonding forces with sulfonate (-SO3H). As can be seen from Fig. 4, when 1 wt% of graphene is introduced into the sulfonated polyamidamine, the -OH group is displaced in the direction of high wave number, so that the existence of hydrogen recognizing force can be confirmed. By this force, the reduced graphene can be uniformly dispersed in the polymer system.
步驟S102、往混合溶液中加入還原劑進行還原反應得到磺化高分子/石墨烯奈米複合材料，所述磺化高分子/石墨烯奈米複合材料包括單層石墨烯和與多層石墨烯均勻分散在磺化高分子。 Step S102, adding a reducing agent to the mixed solution for reduction reaction to obtain a sulfonated polymer/graphene nano composite material, wherein the sulfonated polymer/graphene nano composite material comprises a single layer of graphene and is uniform with the multilayer graphene. Dispersed in sulfonated polymer.
優選的，還原劑為聯胺(Hydrazine)。 Preferably, the reducing agent is a hydrazine.
例如，可以在25℃的溫度下，按照氧化石墨烯與聯胺為1g：5mL的比例往混合溶液中加入品質濃度為50%的聯胺，攪拌1分鐘，之後加熱到100℃下回流反應2小時，分離純化，進而得到磺化高分子/石墨烯奈米複合材料。 For example, a bisamine having a mass concentration of 50% may be added to the mixed solution at a temperature of 25 ° C in a ratio of 1 g:5 mL of graphene oxide to hydrazine, stirred for 1 minute, and then heated to reflux at 100 ° C. After hours, separation and purification were carried out to obtain a sulfonated polymer/graphene nano composite.
上述方法中，當氧化石墨烯通過聯胺還原成石墨烯時，由於磺化高分子均勻穿插於氧化石墨烯的層間，因此在進行還原反應時，磺化高分子不會被石墨烯所排擠，因此能大幅增加石墨烯添加於高分子中的比 例。另外，上述方法的特點為一步反應生成奈米複合材料，而非現有文獻中的先做成石墨烯再添加於高分子中，這不僅僅省去了一個步驟，另外還可以大幅提升石墨烯添加於高分子的比例。 In the above method, when graphene oxide is reduced to graphene by hydrazine, since the sulfonated polymer is uniformly interspersed between the layers of graphene oxide, the sulfonated polymer is not displaced by graphene during the reduction reaction. Therefore, the ratio of graphene added to the polymer can be greatly increased. example. In addition, the above method is characterized by one-step reaction to form a nano composite material, instead of first adding graphene to the polymer in the prior literature, which not only saves one step, but also greatly increases the addition of graphene. The ratio of the polymer.
本實施方式的磺化高分子/石墨烯奈米複合材料具有優良的透光性和導電性，因此可以應用於觸控面板以取代氧化銦錫(ITO)。 The sulfonated polymer/graphene nanocomposite of the present embodiment has excellent light transmittance and conductivity, and thus can be applied to a touch panel to replace indium tin oxide (ITO).
以下通過具體實施例來進一步說明。 The following is further illustrated by the specific examples.
實施例1 Example 1
以0.1wt%石墨烯/礦化聚亞醯胺複合材料為例，首先將10mg氧化石墨烯分散於10ml的去離子水中，進行超聲震盪30分鐘，另外，將磺化聚亞醯胺90mg加入0.45ml的二甲基亞碸(DMSO)，並攪拌30分鐘。之後將氧化石墨烯溶液，慢慢滴入磺化聚亞醯胺溶液內，並持續攪拌15分鐘即可得到混合溶液。然後將約0.05ml品質濃度50%的聯胺加入到混合溶液中，在100℃的溫度下回流反應2小時，使氧化石墨烯還原成石墨烯，然後分離純化，烘乾，得到磺化聚亞醯胺/石墨烯奈米複合材料。 Taking 0.1wt% graphene/mineralized polyamidamine composite as an example, firstly disperse 10mg of graphene oxide in 10ml of deionized water, perform ultrasonic vibration for 30 minutes, and add 90mg of sulfonated polyamidoamine to 0.45. Mol of dimethyl hydrazine (DMSO) was stirred for 30 minutes. Thereafter, the graphene oxide solution was slowly dropped into the sulfonated polyamine reaction solution, and stirring was continued for 15 minutes to obtain a mixed solution. Then, about 0.05 ml of a hydrazine having a mass concentration of 50% is added to the mixed solution, and the reaction is refluxed at a temperature of 100 ° C for 2 hours to reduce the graphene oxide to graphene, and then separated and purified, and dried to obtain a sulfonated polyamide. Indoleamine/graphene nanocomposite.
請參閱圖5，所示為實施例1的磺化磺化聚亞醯胺/石墨烯奈米複合材料的TEM(透射電子顯微鏡)照片。由圖5可知，奈米級的石墨烯均勻分散於磺化磺化聚亞醯胺層間。 Referring to Figure 5, a TEM (transmission electron microscopy) photograph of the sulfonated sulfonated polymethyleneamine/graphene nanocomposite of Example 1 is shown. As can be seen from Fig. 5, the nano-scale graphene is uniformly dispersed between the sulfonated sulfonated polyamidamine layers.
採用Autolab的PGSTAT30型電導率儀測量，本實施例的磺化高分子/石墨烯奈米複合材料的電導率為0.145S/cm。 The conductivity of the sulfonated polymer/graphene nanocomposite of this example was 0.145 S/cm as measured by Autolab's PGSTAT30 conductivity meter.
表1中，未添加石墨烯的磺化聚亞醯胺(SPI)的導電度為0.137S/cm，隨著石墨烯的增加，其導電率也會跟著提升。當石墨烯添加到1wt%時，導電度可達0.361S/cm。相較於未添加石墨烯的磺化聚亞醯胺，SPI/1wt%石墨烯的導電度提高了接近三倍的幅度，因此很明顯的說明石墨烯能有效的提升整體的導電性。 In Table 1, the conductivity of the sulfonated polyiminamide (SPI) to which no graphene is added is 0.137 S/cm, and the electrical conductivity increases as the graphene increases. When graphene is added to 1 wt%, the conductivity can reach 0.361 S/cm. The conductivity of SPI/1wt% graphene is increased by nearly three times compared to the sulfonated polyamidene without graphene added, so it is clear that graphene can effectively improve the overall conductivity.
另外，磺化聚二乙炔/石墨烯，與磺化聚乙烯醇/石墨烯，均可以參照實施例1的步驟得到奈米複合材料。 Further, the sulfonated polydiacetylene/graphene and the sulfonated polyvinyl alcohol/graphene can be obtained by referring to the procedure of Example 1 to obtain a nano composite material.
以上所述實施例僅表達了本發明的幾種實施方式，其描述較為具體和詳細，但並不能因此而理解為對本發明專利範圍的限制。應當指出的是，對於本領域的普通技術人員來說，在不脫離本發明構思的前提下，還可以做出若干變形和改進，這些都屬於本發明的保護範圍。因此，本發明專利的保護範圍應以所附權利要求為准。 The above-mentioned embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.
S101‧‧‧步驟 S101‧‧‧Steps
S102‧‧‧步驟 S102‧‧‧Steps
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