TW201111279A - Method of manufacturing expansion graphite - Google Patents
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201111279 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種石墨之製法，特別是指一種膨脹 型石墨（expandable graphite，EG)之製法。 【先前技術】 膨脹型石墨是一種石墨插層複合物（grapMte intercalation compoundS，GICs)，為利用層間插入處理而將 • 作為膨脹源的化學物質滲浸入天然石墨的層狀結構中，使 膨脹型石墨具有高溫膨脹性能，其特性為在常溫至2〇〇〇c .時為穩定不變形狀態，而且具有抗酸、抗鹼及疏水性，當 受熱咼於200 C時’其層間插入的化學物質會分解生成氣 體而使得石墨膨脹的厚度急遽膨脹至數十乃至數百倍，而 變成體積蓬鬆並具有多孔結構之蠕蟲狀粉末並在燃燒表面 形成阻隔碳層，一方面可吸收輻射熱與隔絕熱能，以阻止 熱量傳送、一方面可吸附燃燒所產生的氣體而抑制可使人 • 窒息的煙塵產生，並降低可燃性氣體濃度，再加上石墨本 身之氣化點超過3000°C以上’足以抵抗一般的火災溫度， 具有多重阻燃效果’一般來說，體積膨脹倍率越高則阻熱 效果越佳’故膨脹型石墨是目前世界上最環保與安全的難 燃劑。 可在石墨層中插入的化學物質如：硝酸鹽類（nitrates)、 硫酸鹽類（sulphates)及氧化物（oxides)等各式分子，其反應式 一般相信為： n C + X AH <-> CnCAH^OA' + H+ + e' 201111279 其中，A代表ΝΟΓ或HS〇r，且η及x為正整數。通常石 墨與硫酸反應會生成C24+HS〇r · 2H2S04，而與硝酸反應生 成 C24+N03-.3HN03。 傳統製備膨脹型石墨的方法有三種： (1) 電化學法，如 Kang等人於期刊 2002，40, p.1575-1578所揭示之製備方法，將平均尺寸為300 μηι 的天然石墨包覆於材質為聚丙稀（polypropylene)之網袋 中，並含浸於93 wt%之硫酸水溶液所組成的電解液中， 並使用不銹鋼材質之陰、陽電極於通電後進行插層硫酸 的電化學反應，其電量耗損率（electricity consumption)介 於10.83-40.00 A hr/kg之間，所得產物之膨脹體積高， 當電量耗損率為40.00 A hr/kg時，可達250 mL/g，但電 化學法是一種較耗能的方法，且因該方式可能會有過度 插層（over-intercalation)的情況，而易導致膨脹型石墨在 室溫下部分體積便會產生膨脹，此會降低膨脹型石墨的 使用效能； (2) 化學浸潰法，為將石墨浸潰於化學氧化劑或強酸中，如201111279 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing graphite, and more particularly to a method for producing expandable graphite (EG). [Prior Art] Intumescent graphite is a kind of graphite intercalation compound (GICs), which is used to infiltrate a chemical substance as an expansion source into a layered structure of natural graphite by interlaminar insertion treatment to make expanded graphite. It has high temperature expansion property and its characteristics are stable and non-deformed at room temperature to 2〇〇〇c. It has acid resistance, alkali resistance and hydrophobicity. When heated to 200 C, the chemical substances inserted between the layers will be Decomposing the gas to cause the thickness of the graphite to expand rapidly to tens or even hundreds of times, and become a bulky and worm-like powder with a porous structure and forming a barrier carbon layer on the combustion surface, on the one hand, absorbing radiant heat and insulating heat, In order to prevent heat transfer, on the one hand, it can adsorb the gas generated by combustion, suppress the generation of smoke that can cause suffocation, and reduce the concentration of flammable gas, and the vaporization point of graphite itself exceeds 3000 ° C or more 'sufficient to resist general Fire temperature, with multiple flame retardant effects 'In general, the higher the volume expansion ratio, the better the heat resistance effect' Intumescent graphite is the world's most environmentally friendly flame retardants and security difficult. Chemicals that can be inserted into the graphite layer, such as nitrates, sulphates, and oxides, are generally believed to be: n C + X AH <- > CnCAH^OA' + H+ + e' 201111279 where A represents ΝΟΓ or HS〇r, and η and x are positive integers. Usually, graphite reacts with sulfuric acid to form C24+HS〇r · 2H2S04, and reacts with nitric acid to form C24+N03-.3HN03. There are three conventional methods for preparing expanded graphite: (1) Electrochemical methods, such as the method disclosed by Kang et al., 2002, 40, p. 1575-1578, coating natural graphite having an average size of 300 μηι The material is a polypropylene mesh bag, and is impregnated with an electrolyte composed of 93 wt% of sulfuric acid aqueous solution, and an electrochemical reaction of intercalating sulfuric acid is performed after energization using a stainless steel anode and an anode electrode. The electricity consumption rate is between 10.83-40.00 A hr/kg, and the expanded volume of the obtained product is high. When the power consumption rate is 40.00 A hr/kg, it can reach 250 mL/g, but the electrochemical method is A more energy-intensive method, and there may be over-intercalation in this way, which tends to cause expansion of the expanded graphite at room temperature, which reduces the use of expanded graphite. (2) Chemical immersion method for immersing graphite in chemical oxidants or strong acids, such as
Ji-hui Li 等人於期刊 2006，60，ρ·746- 749揭示以醋酸酐（acetic anhydride)為插層劑（inserting agent)及重絡酸舒（potassium dichromate)為氧化劑，並加 入濃硫酸於溫度介於25〜65°C下與直徑小於160 μηι的 天然石墨進行反應，所得產物之膨脹體積介於 30〜60mL/g之間，因該方法為一開放性的操作環境，當 含有強氧化劑及強酸等水溶液經加熱後，易導致蒸氣的 201111279 逸散’不僅容易造成環境的污染，且由於溶液蒸氣遷的 限制而無法提高加熱溫度，以增加反應的效率，且發現 當提高濃硫酸的加入量時，雖然使得硫酸亦具有插層劑 的效果，以增加石墨層間的插層劑含量（即插層率），但 也由於強酸和氧化劑的含量極高，而造成石墨的過度氧 • 化此可旎會影響膨脹型石墨的機械強度或其他物理特 性，而限制膨脹型石墨的應用性；以及 • (3)超音波震盈法，如Li等人於期刊M浙油 2007’ 61，p.5070-5073揭示使用有機溶劑（如甲酸 、乙醇、醋酸等）或無機溶劑（如鹽酸、磷酸 '硝酸等）， 分別於250 W及500 W的不同超音波功率下與平均尺寸 為320 μιη的天然石墨進行反應，但所製得產物之膨脹 體皆不高，惟當使用無機溶劑如硝酸時，所得產物才具 有較高的膨脹體積（43〜60 mL/g)，且該方法亦是一種較 耗能的方法。 • 由上述可知，現有的膨脹型石墨之製備仍有需要發展 出一種兼具有製程及設備簡單、成本低，且插層效果佳的 方法，以提咼能源以及反應物運用之效率。 【發明内容】 鑒於用以製備膨脹型石墨的反應物大多為具有強氧化 性、強酸性，且需要外加能量以在石墨層間插入化學物質 ，若要使得插層劑能更有效地與石墨進行反應，又能兼顧 降低環境的/亏染與能源的消耗，因此本案發明人嘗試以相 201111279 近似於水熱法（hydrothermal method)的方式進行膨脹型石 墨的製備與研發。 水熱法是加熱於水溶液系統的一種反應方式，可以製 備的種類大多限於金屬、氧化物和複合氧化物在内的多種 粉末，所製得之產物具有結晶度佳、純度高，粒徑小且分 佈均勻等優點’如US 7,267,812揭示使用水熱法於 100 200 c下反應1 ~3天，可製備結合不同孔徑類型以及結 晶度高之含有氧化矽（Si〇2)及氧化鋁（Abo〗）複合成分的沸石 因此，本發明之一目的，即在提供一種膨脹型石墨之 氧化劑與水進行混合，以獲得— 製法，係包含 使一石墨、一插層劑 混合物；以及 於-密閉環境下，使該混合物進行加熱，以製得該膨服型 石墨。 本發明膨脹型石墨之製法為利用水熱法的原理，先將 ，-石墨、-插層劑、一氧化劑與水進行充分地混合後，將 邊含有固、液二相的混合物置於一密閉的環境中並加埶， 在適當的條件控制下，#由該氧化劑的作㈣分開石墨之 層與層_妒弱鍵結，且該插層劑亦分解成的活化的離子 癌，另—方面，於該密閉環境中加熱所產生的内部高壓能 應液體的蒸氣壓以降低汽化的情形，並避免反應溶 =的逸放，本發明成功將傳統用於㈣金屬、氧化物 合乳化物的水詩實驗料作料 201111279 化反應主要作用於分開石墨的層間鍵結上，並操取水熱法 之活化離子在密閉環境下可進行有序排列以形成結晶粉末 的原理，使得插層劑之活化離子可以有序地以插層方式重 新排列於石墨層間，可有效提高石墨層間的插層率。 本發明膨脹型石墨之製法的功效在於：相較於傳統的 電化子法可減少能源的消耗，並避免石墨的過度氧化，而 f發明製法係於—密閉環境中進行，故相較於傳統的化學 心製法，可避免含有強酸及強氧化物質之反應溶液的逸散 ’以減少環境的污染，I因反應的溫度較高，可提高反應 的效率與活化離子於石墨層間的插層與有序排列，此點亦 可改善以傳統超音波震盪法製得產物之膨脹體積不高的缺 "x1昇工業上製備膨脹型石墨之產量以及產品的穩定 性。 〜 【實施方式】 有關本發明之前述及其他技術内容、特點與功效，在 以下將進—步於實施方式與其等之實施例的詳細說明中， 將可清楚的呈現。 因本製法的插層劑及氧化劑於水的存在下進行混合時 會有放熱的現象產生，為避免於混合的過程中因溫度增加 而使得石墨產生部分氧化，較佳地，該進行混合的溫度是 控制在介於25〜40oC之間。 較佳地，該石墨係先加入插層劑及水，待混合均勻後 ’再加入氧化能力較強的氧化劑，以降低石墨於混合過程 中可能產生的部分氧化之機率。 201111279 較佳地’該含有固、液二相的混合物先利用超音波震 盪的方式’以去除於混合過程中可能溶入的氣體分子，且 在微觀上’經由超音波震盪所提供的能量以增加反應物分 子的動能’以達到均勻混合的目的。 較佳地’本製法的加熱溫度是介於8〇〜200〇c之間。更 佳地，該加熱的溫度是介於8〇〜14〇〇c之間。 車父佳地’該加熱步驟是在一高壓釜中進行，以形成一 密閉之環境。 較佳地’該插層劑與氧化劑之莫耳數比例是介於1 : 1 〜22.6 . 1之間。更佳地，該莫耳數比是4 5 : i。 較佳地=，該插層劑是擇自於硫酸、過氯酸、磷酸、鹽 酸、雙氧水’或此等之_組合。更佳&，該插層劑是硫酸 較佳地，6亥氧化劑是擇自於硝酸、過猛酸鉀' 雙氧水 重鉻酉夂钟臭氧、氣酸鉀、過氣酸钟、硝，酸卸，或此等 之組s。更佳地，該氧化劑是硝酸。 於本發明之具體例中，該插層劑及氧化劑可先分別溶 於水中’當插層劑為硫酸且氧化劑為硝酸日寺，以下列所述 的濃度範圍的水溶㈣式以—體積比例與石墨進行混合， 亦可達成本發明製法之反應物莫耳數比例的較佳及最佳範 圍主張： 水溶液之濃度分別是 且該硫酸水溶液與硝 1之間。更佳地，所 較佳地，所使用的硫酸水溶液及硝酸 介於75〜98 wt%及65〜85 wt%之間， 酸水溶液之體積比例是介於i :〜2〇: 201111279 使用的硫酸水溶液及确酸水溶液之濃度分別是介於93~98 wt%及68〜73 wt%之間，且該硫酸水溶液與硝酸水溶液之 體積比例是4 : 1。 本發明將就以下實施例來作進一步說明，但應瞭解的 是，該等實施例僅為例示說明之用，而不應被解釋為本發明 實施之限制。 特別說明的是，本案發明人已試驗以不同濃度之硫酸 水溶液與硝酸水溶液應用於本發明方法中，但為易於比較其 他較主要之變因（如莫耳數比或體積比例、反應溫度、反應 時間等）’故取以下分別使用相同濃度的硫酸水溶液（95 7Ji-hui Li et al., Journal, 2006, 60, ρ. 746-749 discloses the use of acetic anhydride as an inserting agent and a potassium dichromate as an oxidizing agent, and adding concentrated sulfuric acid to The reaction is carried out at a temperature of 25 to 65 ° C with natural graphite having a diameter of less than 160 μηι, and the resulting product has an expansion volume of between 30 and 60 mL/g, since the method is an open operating environment and contains a strong oxidizing agent. After heating and other aqueous solutions such as strong acid, it is easy to cause the 201111279 of the vapor to escape, which is not only easy to cause environmental pollution, but also cannot increase the heating temperature due to the limitation of the vapor migration of the solution, so as to increase the efficiency of the reaction, and it is found that when the concentrated sulfuric acid is added, In the amount, although the sulfuric acid also has the effect of intercalating agent to increase the intercalation agent content (ie intercalation rate) between the graphite layers, but also due to the high content of strong acid and oxidant, the excessive oxygen of the graphite It can affect the mechanical strength or other physical properties of expanded graphite and limit the applicability of expanded graphite; and • (3) Ultrasonic seismic method, such as Li et al. M. Zhejiang 2007' 61, p.5070-5073 discloses the use of organic solvents (such as formic acid, ethanol, acetic acid, etc.) or inorganic solvents (such as hydrochloric acid, phosphoric acid 'nitric acid, etc.), different ultrasonic waves at 250 W and 500 W, respectively. The natural graphite with an average size of 320 μηη is reacted under power, but the expanded body of the obtained product is not high, but when an inorganic solvent such as nitric acid is used, the obtained product has a high expansion volume (43 to 60 mL/ g), and the method is also a more energy-intensive method. • As can be seen from the above, there is still a need to develop a method for preparing expanded graphite which has both process and equipment, low cost, and excellent intercalation effect, in order to improve the efficiency of energy utilization and reactant utilization. SUMMARY OF THE INVENTION In view of the fact that the reactants used to prepare the expanded graphite are mostly strongly oxidizing, strongly acidic, and require additional energy to insert chemicals between the graphite layers, the intercalating agent can be more efficiently reacted with graphite. In addition, the environmental impact/loss and energy consumption can be reduced. Therefore, the inventors of the present invention attempted to prepare and develop the expanded graphite by the method of 201111279 which is similar to the hydrothermal method. The hydrothermal method is a reaction method of heating in an aqueous solution system, and most of the types that can be prepared are limited to various powders including metals, oxides, and composite oxides, and the obtained products have good crystallinity, high purity, and small particle size. The advantages of uniform distribution, such as US 7,267,812, reveal that the reaction with hydrothermal method at 100 200 c for 1-3 days can be combined with different pore size types and high crystallinity containing cerium oxide (Si〇2) and alumina (Abo). Zeolite of composite component, therefore, an object of the present invention is to provide an oxidizing agent for expanding graphite and water to obtain a method comprising: forming a graphite, an intercalant mixture; and in a closed atmosphere, The mixture was heated to obtain the expanded graphite. The method for preparing the expanded graphite of the present invention is to utilize the principle of hydrothermal method, and firstly, the graphite, the intercalation agent, the oxidant and the water are thoroughly mixed, and then the mixture containing the solid phase and the liquid phase is placed in a closed state. In the environment, and under the control of appropriate conditions, the oxidant is used to separate the layer of graphite from the layer _ 妒 weak bond, and the intercalant is also decomposed into activated ionic cancer, another aspect The internal high pressure energy generated by heating in the closed environment should reduce the vapor pressure of the liquid to reduce the vaporization condition, and avoid the escape of the reaction solution. The present invention successfully uses the water conventionally used for the (IV) metal and oxide emulsion. Poetry experiment material 201111279 The chemical reaction mainly acts on separating the interlayer bonds of graphite, and the principle that the activated ions of hydrothermal method can be arranged in order to form crystalline powder in a closed environment, so that the activated ions of the intercalating agent can be Orderly re-arranged between the graphite layers by intercalation can effectively improve the intercalation rate between the graphite layers. The effect of the method for producing expanded graphite of the present invention is that the energy consumption can be reduced and the excessive oxidation of graphite can be avoided compared with the conventional electrochemical method, and the method of the invention is carried out in a closed environment, so that compared with the conventional The chemical heart method can avoid the escape of the reaction solution containing strong acid and strong oxidizing substances to reduce environmental pollution. I can increase the efficiency of the reaction and the intercalation and ordering of the activated ions between the graphite layers due to the higher temperature of the reaction. Arrangement, this point can also improve the production volume of the expanded graphite produced by the conventional ultrasonic oscillating method, and the stability of the product. The above and other technical contents, features and effects of the present invention will be apparent from the following detailed description of the embodiments and the embodiments. When the intercalation agent and the oxidizing agent of the present process are mixed in the presence of water, an exothermic phenomenon occurs, and in order to avoid partial oxidation of the graphite due to an increase in temperature during the mixing, preferably, the temperature at which the mixing is performed is performed. Is controlled between 25~40oC. Preferably, the graphite is first added with an intercalant and water, and after being uniformly mixed, an oxidizing agent having a strong oxidizing ability is added to reduce the probability of partial oxidation of graphite which may occur during the mixing process. 201111279 Preferably, the mixture containing solid and liquid phases first utilizes ultrasonic oscillating mode to remove gas molecules that may be dissolved during the mixing process, and microscopically increase the energy provided by ultrasonic oscillations. The kinetic energy of the reactant molecules 'to achieve the purpose of uniform mixing. Preferably, the heating temperature of the present process is between 8 Å and 200 Å. More preferably, the heating temperature is between 8 Torr and 14 Torr. The rider's heating step is carried out in an autoclave to form a closed environment. Preferably, the molar ratio of the intercalant to the oxidant is between 1:1 and 22.6.1. More preferably, the molar ratio is 4 5 : i. Preferably, the intercalant is selected from the group consisting of sulfuric acid, perchloric acid, phosphoric acid, hydrochloric acid, hydrogen peroxide, or the like. More preferably, the intercalant is sulfuric acid, and the 6 oxidant is selected from the group consisting of nitric acid, potassium perchlorate, hydrogen peroxide, heavy chrome, ozone, potassium sulphate, gas, acid, acid , or the group of these. More preferably, the oxidizing agent is nitric acid. In a specific example of the present invention, the intercalating agent and the oxidizing agent may be separately dissolved in water respectively. 'When the intercalating agent is sulfuric acid and the oxidizing agent is nitric acid, the water-soluble (four) formula in the concentration range described below is in a volume ratio The graphite is mixed to achieve a preferred and optimal range of the molar ratio of the reactants of the process of the present invention. The concentration of the aqueous solution is between and between the aqueous sulfuric acid solution and the nitrate 1. More preferably, preferably, the aqueous sulfuric acid solution and the nitric acid used are between 75 and 98 wt% and 65 to 85 wt%, and the volume ratio of the aqueous acid solution is between i:~2〇: 201111279 used sulfuric acid The concentration of the aqueous solution and the aqueous acid solution is between 93 and 98 wt% and between 68 and 73 wt%, respectively, and the volume ratio of the aqueous sulfuric acid solution to the aqueous nitric acid solution is 4:1. The invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting. In particular, the inventors of the present invention have tried to apply different concentrations of aqueous sulfuric acid solution and aqueous solution of nitric acid to the method of the present invention, but it is easy to compare other major causes (such as molar ratio or volume ratio, reaction temperature, reaction). Time, etc.' Therefore, the following concentrations of sulfuric acid aqueous solution were used separately (95 7
Wt /〇)、石肖酸水溶液（7〇 進行反應所製得的一系列實驗結 果作為例示，但不應以此濃度為限，只要是使用符合上述較 佳莫耳數比範圍的反應物組合或符合上述濃度範圍中的溶液 濃度皆可。 <實施例1> 取5g的天然鱗片石墨（natural以匕graphite，純度99%, 粒徑大小為192.5//m,由國碳公司提供）與2〇mL濃度為 95.7 wt%之硫酸水溶液先行混合攪拌5分鐘後，在低於 4〇 C的溫度下逐漸滴入5mL濃度為7〇 之硝酸水溶液， 即硫酸水溶液及硝酸水溶液是以4:丨的體積比例與天然鱗 片石墨進行混合，以獲得一含插層劑（即硫酸）與氧化劑（即 确酸）之莫耳數比為4.5 : 1之混合物。如圖1所示，將該混 合物倒入一鐵氟龍（Teflon®)製的容器】中，再利用超音波震 201111279 盪器以600 W之功率震盪3〇分鐘之後，將該裝有反應混合 物（圖未示）的鐵氟龍容器！並鎖緊上蓋n，放入一 ^壓釜 (aUt〇clave)2中並密封，接著置於溫度設定為8〇〇c之烘箱内 ，以進行石墨插層之化學反應！小時，之後移出該高壓爸2 ，待冷卻過後加入大量之去離子水進行過濾清洗，以移除 未反應之多餘的酸液，之後放置於室溫（約25〇(：)下工天， 再放入溫度設定為80°C之烘箱内，乾燥1小時後，即得到 膨脹型石墨。 [X-光粉末繞射分析（x_ray powder diffracd〇n，xrd)] 天然鱗片石墨之晶體結構是具有碳六角型平面堆積而 成的層狀結構’分別取天朗片石墨、實施例丨之膨脹型 石墨以及實施例上之膨服型石墨經過iQQ()c3d秒㈣ ^後所形成的已膨脹石墨，進行χ•光粉末繞射分析（χ-_ 先源為銅乾材，操作電壓35 kv，操作電流為3〇誕，繞射 2 2度掃晦到80度)以測定各測試樣品之石墨晶體結構的 : 由圖2之結果可以得知：天然鱗片石墨之曲線⑷ 有^個強烈反料…個位於2Θ=26 56。域 〇利用之公式代入（η為正整數，且η>2又 計算可得d(即層間距）=0·344 _，另一個位於 石墨之^^波峰，則料算可得㈣.188⑽，·膨服型 ，2Θ_ ‘，（）中’二個特性波♦有明顯偏移的現象，其中 即声門靜Γ皮峰Μ，另—個料則偏移至胸5.8卜 “為d=0.354 nm’此證明石墨經插層反應後會 10 201111279 增加層狀結構中的層間距；而由曲線⑷中的特性波峰 2Θ=26·47。接近未插層之石墨的2Θ=26 56。波峰，則表示燃燒 處理會使得原本插層進入石墨中的硫酸根離子遇高溫後釋 出，而使得已膨脹石墨（expanded graphite)的層間距變小至 接近未進行插層前之值，但亦可以清楚發現缺少2θ=5465〇 的特性吸收峰’此現象表示膨脹過後之石墨結構堆積較為 鬆散且呈現不規則狀。 [傅立葉紅外線偵測光譜（FT_IR)] 由圖3之FT-IR光譜可看出，相較於天然鱗片石墨之吸 收波峰的分佈，與硫酸水溶液進行插層反應所得之膨脹型 石墨的光譜會出現·0Η (335〇 cm-丨）與c=s (12〇〇 cm’二種官 月匕基之特性波峰，證明使用硫酸之插層反應亦會產生c與$ 原子的鍵結以及代表插層成功之膨脹型石墨之層間所含的 硫酸根（HSO4—)或硫酸㈤⑽4)之_〇h官能基。 [拉曼（Raman)光譜] 經由拉曼光譜的分析可以定量出每個鍵結中的含量， 在圖4中，位於丨58〇 cm-丨的特性波峰稱為G_band，屬於石 墨中奴原子架構的完整型態（sp2鍵結，類似於苯環上的 鍵結），而位於1350 cm·1的特性波峰則稱為D_band，屬於 不完整型態的碳原子架構（屬於c_c鍵結），以拉曼光譜可以 明顯的觀察出，相較於天然鱗片石墨之光譜，膨脹型石墨 經過插層反應後有較多不規則之波峰產生。利用G-band點 與D-band的面積積分比值（G-band/D_band)，亦可以看出相 較於天然鱗片石墨具有的完整之碳原子架構比例（G_band/D_ 11 201111279 band-1’33)，膨脹型石墨會因為酸根的插層而使得完整的碳 原子架構之比例明顯降低（G-band/D-band=l. 16)，此證明本 發明方法的插層效果顯著。 [掃描式電子顯微鏡（SEM)] 藉由掃描式電子顯微鏡（JEOL-JSM-7401F)可以更清楚 觀察到天然石墨、膨脹型石墨及燃燒過後知已膨脹石墨不 同之表面外觀形態（morPh〇l〇gy)(拍攝倍率為xl0,0〇〇或 x250)。由圖5的結果中，可觀察到天然鱗片石墨（a)具有很 規則且緊密堆疊之層狀結構；經由酸插層過後的膨脹型石 墨（b)則可看到表面出現有不規則之變化；經燃燒過後，已 膝脹石墨（c)可看到表面因插層間的體積膨脹形成開口，而 產生類似豆莢狀的表面形態，其在較低倍率（X25〇)下看來 (d)則呈現蠕蟲狀的形態。 <實施例2〜23> 實施例2〜23為以與實施例！相同的操作方式製備一系 列本發明膨脹型石墨’不同之處在於： ⑴使用之硫酸水溶液及硝酸水溶液的體積比（h2S〇4 : HN〇3)為 3 : 1、2 : 1、1 :卜 5 : 1、10 : i、15 : i 或 20 : 1 ; (Π)進行插層反應之設定溫度為1〇〇c>c、12〇。匚或 140oC ;及 (iii)進行插層反應之時間為3〇、12〇或18〇分鐘； 12 201111279 各實施例之反應條件整理如下表1所示 表1 ·A series of experimental results obtained by carrying out the reaction of Wt / 〇) and aqueous solution of tartaric acid (7 作为 as an example, but should not be limited to this concentration, as long as a combination of reactants meeting the above preferred range of molar ratios is used. Or the concentration of the solution in the above concentration range is acceptable. <Example 1> 5 g of natural flake graphite (natural 匕graphite, purity 99%, particle size 192.5 / / m, supplied by the National Carbon Company) and 2 〇mL concentration of 95.7 wt% of sulfuric acid aqueous solution was mixed and stirred for 5 minutes, then gradually dropped 5 mL of a 7 〇 aqueous solution of nitric acid at a temperature lower than 4 〇C, ie, the aqueous solution of sulfuric acid and the aqueous solution of nitric acid were 4:丨The volume ratio is mixed with natural flake graphite to obtain a mixture containing an intercalant (i.e., sulfuric acid) and an oxidizing agent (i.e., acid) having a molar ratio of 4.5: 1. As shown in Figure 1, the mixture is poured. In a Teflon® container, the Teflon container containing the reaction mixture (not shown) is oscillated at 600 W for 3 minutes using an ultrasonic shock 201111279. And lock the cover n and put it in ^A pressurization (aUt〇clave) 2 and sealed, and then placed in an oven set to 8 〇〇c to carry out the chemical reaction of graphite intercalation! Hours, then remove the high pressure dad 2, add a large amount after cooling The deionized water is filtered and washed to remove the unreacted excess acid solution, and then placed at room temperature (about 25 〇 (:) for working days, then placed in an oven set to 80 ° C, drying 1 After an hour, the expanded graphite is obtained. [X-ray powder diffracd〇n, xrd] The crystal structure of natural flake graphite is a layered structure with carbon hexagonal planes stacked. Longitudinal graphite, the expanded graphite of the example, and the expanded graphite of the example of the expanded graphite formed by iQQ()c3d seconds(4)^, for the diffraction analysis of the χ•光 powder (χ-_ For dry copper, the operating voltage is 35 kv, the operating current is 3 ,, and the diffraction is 2 2 degrees to 80 degrees) to determine the graphite crystal structure of each test sample: It can be known from the results of Figure 2: natural scales The curve of graphite (4) has a strong anti-material... one at 2Θ=26 56 The domain 〇 uses the formula to substitute (η is a positive integer, and η> 2 calculates the available d (ie, the layer spacing) = 0.344 _, and the other is located in the ^ ^ peak of graphite, it is expected to be available (four). 188 (10) , · Expanding type, 2Θ _ ', () in the 'two characteristic waves ♦ there is a significant shift phenomenon, which is the glottal quiet skin peak Μ, the other material is offset to the chest 5.8 卜 "for d = 0.354 Nm' This proves that after the intercalation reaction of graphite, 10 201111279 increases the layer spacing in the layered structure; and the characteristic peak in the curve (4) is 2Θ=26·47. 2 Θ = 26 56 close to unintercalated graphite. The peak indicates that the combustion treatment will cause the sulfate ions originally inserted into the graphite to be released after the high temperature, so that the interlayer spacing of the expanded graphite becomes smaller to the value before the intercalation, but also It can be clearly found that the characteristic absorption peak lacking 2θ=5465〇' indicates that the graphite structure after expansion is loose and irregular. [Fourier Infrared Detection Spectroscopy (FT_IR)] It can be seen from the FT-IR spectrum of Fig. 3 that the spectrum of the expanded graphite obtained by intercalation reaction with aqueous sulfuric acid solution appears in comparison with the distribution of absorption peaks of natural flake graphite. · 0Η (335〇cm-丨) and c=s (12〇〇cm' characteristic peaks of the two kinds of sulphate, which proves that the intercalation reaction using sulfuric acid also produces the bond of c and $ atoms and represents the intercalation Sulfate (HSO4-) or sulfuric acid (5) (10) 4) _ 〇 h functional group contained between layers of successful expanded graphite. [Raman spectrum] The content of each bond can be quantified by Raman spectroscopy. In Fig. 4, the characteristic peak at 丨58〇cm-丨 is called G_band, which belongs to the slave atomic structure in graphite. The complete form (sp2 bond, similar to the bond on the benzene ring), and the characteristic peak at 1350 cm·1 is called D_band, which is an incomplete type of carbon atom structure (belonging to c_c bond), Raman spectroscopy can clearly observe that compared with the spectrum of natural flake graphite, the expanded graphite has more irregular peaks after intercalation reaction. Using the area-integral ratio of G-band point to D-band (G-band/D_band), it is also possible to see the complete carbon atomic architecture ratio compared to natural flake graphite (G_band/D_ 11 201111279 band-1'33 ), the expanded graphite will significantly reduce the proportion of the complete carbon atom structure due to the intercalation of the acid radicals (G-band/D-band = 1.6), which proves that the intercalation effect of the method of the present invention is remarkable. [Scanning Electron Microscopy (SEM)] The surface appearance of natural graphite, expanded graphite, and expanded graphite after combustion can be more clearly observed by scanning electron microscopy (JEOL-JSM-7401F) (morPh〇l〇gy ) (The shooting magnification is xl0, 0〇〇 or x250). From the results of Fig. 5, it can be observed that the natural flake graphite (a) has a layered structure which is very regular and closely packed; the expanded graphite (b) after the acid intercalation can be seen to have irregular changes in the surface. After combustion, the knee-expanded graphite (c) can be seen to form an opening due to the volume expansion between the intercalations, resulting in a pod-like surface morphology, which appears at a lower magnification (X25〇) (d) It presents a worm-like morphology. <Examples 2 to 23> Examples 2 to 23 are the same as the examples! The same operation mode is used to prepare a series of expanded graphite of the present invention. The difference is as follows: (1) The volume ratio of the aqueous sulfuric acid solution and the aqueous nitric acid solution (h2S〇4: HN〇3) is 3:1, 2:1, 1 : 5 : 1, 10 : i, 15 : i or 20 : 1 ; (Π) The set temperature for the intercalation reaction is 1〇〇c>c, 12〇.匚 or 140oC; and (iii) The time for the intercalation reaction is 3〇, 12〇 or 18〇 minutes; 12 201111279 The reaction conditions of the respective examples are as shown in Table 1 below.
條件 實施例 H2S〇4 : HNO, 時間（分鐘） ^ 一 體積比 莫耳- 數比 1 4.5 4 1 ：1 80 2 3 1 3.4 1 80 60 3 2 1 2.3 1 80 60 4 1 1 1.1 1 8〇 60 5 5 1 5^ 1 80 ή0 6 10 1 11.3 1 — 80 6〇____ 7 15 1 16.9 1 80 8 20 1 22.6 1 80 —-ή〇 9 4 1 4.5 1 ———— 80 10 4 1 4.5 1 80 jy-^^ 1 ?〇 11 4 1 4.5 1 80 180 12 4 1 4.5 1 100 3〇___— 13 4 1 4.5 1 100 14 4 1 4.5 1 100 jy---- 1 ?〇 15 4 1 4.5 1 J 100 180 16 4 1 4.5 1 120 17 「4 1 4.5 1 120 60__ 18 4 1 4.5 1 120 —-1 20 19 4 1 4.5 1 120 Jjy- 180____ 20 4 1 4.5 1 140 3〇___ 21 4 1 4.5 1 140 -—--- ή〇 22 4 1 4.5 1 140 i 9〇 23 4:1 4.5 1 140 1 Z v -- 180___ <比較例1~4> 比較例卜4之膨脹型石墨，是取5g的天然鱗片石墨加 入濃度為95_7wt%之硫酸水溶液及濃度為7〇^%之硝酸水 溶液.，與實施爿1相同的反應物條件，分別以不同之體積 比例先U授拌5分鐘後’以習知之超音波震i方法利 用超音波震盪器以6〇〇 w之功率於室溫（約為25。〇下震盪 30分鐘以製備一系列之膨脹型石墨，之後加入大量之施 13 201111279 ，並放置 之烘箱内 子水進行過濾清洗，以移除未反應之多餘的酸液 於室溫（約25 C)下1天，再放入溫度設定為8〇。口 乾燥1小時後’即得到膨脹型石墨，其中，比較例卜4 所使用之硫酸水洛液及硝酸水溶液的體積比（H2S〇4 : hn〇3) 分別是4 : 1 (比較例1)、3 : i (比較例2)、2 : i (比較例” 以及1 : 1 (比較例4)。 |測試結果| [體積膨脹倍率] 將實施例1〜23及比較例卜4所得之膨脹型石墨進行 1000 C、30移的燃燒處理，測量各組膨脹型石墨受熱前的 單位重里之體積（各組相近，皆為3 mL/g)、受熱後所形成的 已膨脹石4的單位重量之體積（mL/g)，經計算得各樣品之體 積膨脹倍率（expanded rati〇)之數據結果如下表2及3所示。 由表2之實施例1〜4與比較例丨〜4之結果，可明顯看出以 本發明方法與習知之超音波震盪法分別進行石墨之插層反 應所製得之膨脹型石墨，發現使用相同體積比之硫酸水溶 液及硝酸水溶液之實施例產品較比較例產品具有較高的膨 脹效果。 由表3之實施例5〜8的結果，可看出當反應溫度為 8〇 C及反應時間為6〇分鐘之操作條件下，提高硫酸水溶液 體積比所製得之膨脹型石墨，經加熱後的體積膨脹倍率亦 有隨之增加的情形，而當硫酸水溶液及硝酸水溶液的體積 比呵於15 : 1(即插層劑與氧化劑之莫耳數比為u : 〇之 後，該增加的趨勢則明顯趨缓；而當硫酸水溶液及硝酸水 14 201111279 溶液的體積比為20 : 1(即插層劑與氧化劑之莫耳數比為 22.6 . 1 )，經_加熱後的體積膨脹倍率便達到該操作條件下之 一極限值（25.3)。由實施例9〜23之結果，則可看出當反應 溫度超過80°C之產物的膨脹效果反而一直下降，當反應溫 度設於140°C時，膨脹效果是最差的，可能是當溫度過高 時會破壞石墨之插層結構，導致膨脹效果不佳；另一方面 ’當反應時間過長，即高壓爸一直處於反應設定的高溫中 ，使得高壓釜内壓力隨著時間的增加而過大，亦會導致反 應形成的膨脹型石墨結構遭到破壞，則測試所得的膨脹倍 率反而沒有預期中的效果好。此結果亦顯示當硫酸水溶液 與硝酸水溶液比例4 : 1時，溫度設於80°C、時間60分鐘（ 實施例1)，即可得到具有最佳之膨脹倍率的產物。 表2. 4:1 3:1 2:1 1:1 實施例 1 比較例 1 實施例 2 比較例 2 實施例 3 比較例 3 實施例 4 比較例 4 單位重量之體積 (mL/g) 62 35 46 29 36 22 24 14 體積膨脹倍率 20.67 11.67 15.33 9.67 12.00 7.33 8.00 4.67 表3. 5 6 7 8 9 10 11 12 13 14 單位重量之體積 (mL/g) 69 74 76 76 56 37 37 41 42 36 體積膨脹倍率 23.0 24.7 25.3 25.3 18.7 12.3 12.3 13.7 14.0 12.0 15 201111279Conditional Example H2S〇4: HNO, time (minutes) ^ One volume to molar ratio - 1 4.5 4 1 :1 80 2 3 1 3.4 1 80 60 3 2 1 2.3 1 80 60 4 1 1 1.1 1 8〇 60 5 5 1 5^ 1 80 ή0 6 10 1 11.3 1 — 80 6〇____ 7 15 1 16.9 1 80 8 20 1 22.6 1 80 —-ή〇9 4 1 4.5 1 ———— 80 10 4 1 4.5 1 80 jy-^^ 1 ?〇11 4 1 4.5 1 80 180 12 4 1 4.5 1 100 3〇___— 13 4 1 4.5 1 100 14 4 1 4.5 1 100 jy---- 1 ?〇15 4 1 4.5 1 J 100 180 16 4 1 4.5 1 120 17 "4 1 4.5 1 120 60__ 18 4 1 4.5 1 120 —-1 20 19 4 1 4.5 1 120 Jjy- 180____ 20 4 1 4.5 1 140 3〇___ 21 4 1 4.5 1 140 -—--- ή〇22 4 1 4.5 1 140 i 9〇23 4:1 4.5 1 140 1 Z v -- 180___ <Comparative Example 1~4> Comparative Example 4 of expanded graphite, 5g of natural flake graphite is added to a concentration of 95_7wt% sulfuric acid aqueous solution and a concentration of 7〇%% aqueous nitric acid solution. The same reaction conditions as in the implementation of 爿1, respectively, in different volume ratios, first U mix for 5 minutes. 'Using the ultrasonic vibration method of the conventional ultrasonic wave oscillator to 6〇〇 The power of w is tempered at room temperature (about 25 〇 under the arm for 30 minutes to prepare a series of expanded graphite, then add a large amount of 13 201111279, and placed in the oven water for filtration cleaning to remove unreacted excess The acid solution was allowed to stand at room temperature (about 25 C) for 1 day, and then the temperature was set to 8 Torr. After drying for 1 hour, the expanded graphite was obtained, and the sulphuric acid water solution used in Comparative Example 4 and The volume ratio of the aqueous solution of nitric acid (H2S〇4: hn〇3) was 4:1 (Comparative Example 1), 3: i (Comparative Example 2), 2: i (Comparative Example), and 1:1 (Comparative Example 4). [Test Results] [Volume Expansion Ratio] The expanded graphite obtained in Examples 1 to 23 and Comparative Example 4 was subjected to 1000 C and 30-shift combustion treatment, and the volume per unit weight of each group of expanded graphite before heating was measured ( The similarity of each group is 3 mL/g), and the volume per unit weight (mL/g) of the expanded stone 4 formed by heating. The data of the expanded expansion ratio (expanded rati〇) of each sample is calculated as follows Tables 2 and 3 are shown. From the results of Examples 1 to 4 and Comparative Examples 丨 to 4 of Table 2, it is apparent that the expanded graphite obtained by the intercalation reaction of graphite by the method of the present invention and the conventional ultrasonic oscillation method was found to be used. The product of the same volume ratio of the aqueous solution of sulfuric acid and the aqueous solution of nitric acid has a higher expansion effect than the product of the comparative example. From the results of Examples 5 to 8 of Table 3, it can be seen that when the reaction temperature is 8 〇C and the reaction time is 6 〇 minutes, the expanded graphite obtained by increasing the volume ratio of the aqueous solution of sulfuric acid is heated. The volume expansion ratio also increases, and when the volume ratio of the aqueous solution of sulfuric acid and the aqueous solution of nitric acid is 15:1 (that is, the ratio of the molar ratio of the intercalant to the oxidant is u: ,, the increasing trend is Significantly slowed down; and when the volume ratio of the aqueous solution of sulfuric acid and nitric acid 14 201111279 is 20:1 (ie, the ratio of the molar ratio of the intercalant to the oxidant is 22.6.1), the volume expansion ratio after heating is reached. One of the limit values under operating conditions (25.3). From the results of Examples 9 to 23, it can be seen that when the reaction temperature exceeds 80 ° C, the expansion effect of the product is decreased, and when the reaction temperature is set at 140 ° C, The expansion effect is the worst. It may be that when the temperature is too high, the intercalation structure of graphite will be destroyed, resulting in poor expansion effect. On the other hand, when the reaction time is too long, the high pressure dad is always in the high temperature set by the reaction, so that Autoclave internal pressure If the expansion of the graphite structure is too large with time, the expansion graphite structure formed by the reaction is destroyed, and the expansion ratio obtained by the test is not as good as expected. The result also shows that the ratio of the aqueous sulfuric acid solution to the aqueous nitric acid solution is 4:1. When the temperature was set at 80 ° C for 60 minutes (Example 1), the product having the optimum expansion ratio was obtained. Table 2. 4:1 3:1 2:1 1:1 Example 1 Comparative Example 1 Example 2 Comparative Example 2 Example 3 Comparative Example 3 Example 4 Comparative Example 4 Volume by unit weight (mL/g) 62 35 46 29 36 22 24 14 Volume expansion ratio 20.67 11.67 15.33 9.67 12.00 7.33 8.00 4.67 Table 3. 5 6 7 8 9 10 11 12 13 14 Volume per unit weight (mL/g) 69 74 76 76 56 37 37 41 42 36 Volume expansion ratio 23.0 24.7 25.3 25.3 18.7 12.3 12.3 13.7 14.0 12.0 15 201111279
利用又螺幹》昆練機（Plastograph，Brabender)於 . 6〇 ΓΡΠ1>的设定條件下，將上述實施例1所得之膨脹型石墨 、:j、、力入尚雀度}乙稀⑻灿 density polyethylene, HDPE)中， ^此摻的方式均勻混合8分鐘，再將均勻混合後之成塊樣 扣於150 C的設定條件下，以熱壓成型機（fb_6〇t〇n， ^械读堡成尺寸為·xl_mm之複合材料試片，^ =同重買百分率(wt%)之膨脹型石墨所得的試片配方則如 例與應㈣，之後亦進行之：燃特性的比較應用 試。 仃各組^之熱穩定性及難燃性剛 表4.Using the Plastograph, Brabender under the setting conditions of 6 〇ΓΡΠ 1 >, the expanded graphite obtained in the above Example 1, j:, force into the scent} ethyl (8) can Density polyethylene, HDPE), ^This method of mixing is evenly mixed for 8 minutes, and then the uniformly mixed block is buckled under the set condition of 150 C to the hot press forming machine (fb_6〇t〇n, ^ For the composite test piece with the size of xl_mm, the test piece formula obtained by the same weight-buying percentage (wt%) of the expanded graphite is as follows (4), and then the comparison test of the burning characteristics is carried out.热The thermal stability and flame retardancy of each group ^ Table 4.
乂戶不，目的為使用本發明方法所製得之膨脹帮石愛 作為難燃劑以測試HDPE複合材枓之紛組批ω 墨 [熱性質分析] 將混捧後的複合材料試片1〜5以粉碎機處理成碎片 再取約5〜1〇 mg的量放置於熱重量分析儀 16 201111279 (thermogravimetric analyzer, TGA, PE Pyris 1 TGA, Perkin Elmer)的爐管中，並設定以每分鐘10°C的升溫速率在氮氣 中升溫至800°C，以觀察各組複合材料的裂解行為以及焦炭 殘餘率，其分析結果如圖6及圖7所示，由圖6之熱重量 (thermogravimetry，TG)曲線可發現混掺有膨脹型石墨之複合 材料大約在200°C附近就會有裂解行為之產生，這是由於 膨脹型石墨大約在200°C時其層間插入的硫酸根離子分解 生成氣體而脫離，而使得該TG曲線相對於未進行混摻的 HDPE有輕微下降的趨勢，且進一步以不同重量損失來看裂 解趨勢，亦可看出隨著混摻膨脹型石墨的比率增加使得複 合材料的殘餘重量百分率（wt%)也相對隨之提高：另外，從 圖 7 之微分熱重量（derivative thermogravimetry，DTG)曲線 觀察到HDPE最大裂解溫度492°C，當混摻膨脹型石墨之含 量增加時，會使得複合材料的裂解速率有減緩之趨勢（經計 算，為由SSJwt%·。。-1減低至21.0\¥1%.。(^丨），且進一步提 高了最大裂解溫度（15。〇，且由二圖中皆可看出含有40wt% 之膨脹型石墨的複合材料（試片5)之耐燃性改善程度最為明 顯。 [積分程序分解溫度（integral procedure decomposition temperature, IPDT)] IPDT主要是在探討材料熱性質的趨勢，其方法為將上 述複合材料試片1〜5裂解之TG曲線採面積化的積分分數值 比較，藉由Doyle，s方式（Doyle，s method)，並代入TGA測 試之開始溫度（7>30。〇以及終止溫度（Tf=800°C)進行分析與 17 201111279 计异，可得各組配方之IpDT值（。〇，其結果如下表5所示 瓜來說，當起始裂解溫度及焦炭殘餘量愈多時，表示 材料的熱％疋性愈好、耐熱性增加，則值亦愈高，由 表5可看出經膨脹型石墨混摻之材科在8⑼。C時之殘餘量 以及IPDT值都比未進行混摻的Η〇ρΕ還要高，且隨著混摻 路脹型石墨之含量的增加，使得複合材料的熱穩定性亦隨 之明顯提高。. 表5.Seto does not, the purpose is to use the expansion gangue made by the method of the invention as a flame retardant to test the HDPE composite 枓 batch of ω ink [thermal property analysis] will be mixed composite test piece 1~ 5, processed into pieces by a pulverizer and then placed in an amount of about 5 to 1 〇mg in a furnace tube of a thermogravimetric analyzer 16 201111279 (thermogravimetric analyzer, TGA, PE Pyris 1 TGA, Perkin Elmer), and set at 10 per minute. The heating rate of °C was raised to 800 °C in nitrogen to observe the cracking behavior and coke residual ratio of each group of composite materials. The analysis results are shown in Fig. 6 and Fig. 7, and the thermogravimetry (TG) of Fig. 6 The curve shows that the composite material mixed with expanded graphite has a cracking behavior around 200 ° C. This is because the expanded graphite is decomposed into gas by the intercalation of sulfate ions at about 200 ° C. The detachment makes the TG curve slightly lower than that of the undoped HDPE, and further shows the cracking tendency with different weight loss. It can also be seen that the compounding with the ratio of the mixed expanded graphite makes the composite The residual weight percentage (wt%) of the feedstock also increased accordingly: In addition, the maximum cracking temperature of HDPE was observed at 492 °C from the differential thermogravimetry (DTG) curve of Figure 7, when the content of blended expanded graphite increased. At the time, the cracking rate of the composite material tends to slow down (calculated by SSJwt%·-1 to 21.0\¥1%. (^丨), and the maximum cracking temperature is further increased (15. 〇, and it can be seen from both figures that the composite material containing 40% by weight of expanded graphite (test piece 5) has the most improved flame resistance. [Integral procedure decomposition temperature (IPDT)] IPDT mainly The trend of thermal properties of materials is discussed by comparing the integral scores of the TG curves of the composite test pieces 1 to 5, by Doyle, s method (Doyle, s method), and substituting into TGA. The test start temperature (7 > 30. 〇 and the termination temperature (Tf = 800 ° C) were analyzed and compared with 17 201111279, and the IpDT value of each group of formulas was obtained (.〇, the results are shown in Table 5 below. When the initial cracking temperature and coke residual amount are more, the better the heat % enthalpy of the material and the higher the heat resistance, the higher the value. It can be seen from Table 5 that the material of the expanded graphite blending is 8 (9). The residual amount and IPDT value of C are higher than that of 未ρΕ which is not blended, and the thermal stability of the composite is also obviously improved with the increase of the content of the blended graphite. . table 5.
"目前㈣騎測歸㈣的難錢常㈣標準為極限 乳指數（hmiting 〇xygen index，L〇I)與沉肩燃燒測試（垂直"Currently (4) The difficulty of riding the test (4) is often (4) The standard is the limit milk index (hmiting 〇xygen index, L〇I) and the shoulder burning test (vertical
燃燒測試法），其中，g I 4 μ & 虱知數和燃燒性的關係一般區分 為三個等級： L.O.I. L.O.I. L.O.I. 上述複合材料試片 〃 〜可燃性 ^〜25 —自熄性（不易燃燒） 6 '"難燃性 而UL-94燃燒測試之條件為以 燒垂直的樣品’火源燃燒1〇 防火等級（即防火性質為V-0 > 2〇 mm高的火源，自底部燃 毛*兩-欠之後以區分帶測樣品之 > v-2 >未達標準）。 5經測試所得的結果如下表6所 18 201111279 不，當膨脹型石墨含量達到30%時（試片4)，材料就具 熄性之現象產生（LOI數據為25)且UL_94達到νι等級，自 果取好的是膨脹型石墨含量達到4〇%時（試片5卜可測得文 料具有難燃的性質（L0I數據為31)且194可以達到^材 級，可以當成很好之防火材料，因此證明以本發明方法^ 製仟之膨脹型石墨為可有效增進複合材料之難燃性質。' 斤 表6.Combustion test method), wherein the relationship between g I 4 μ & 虱 knowing and flammability is generally divided into three grades: LOILOILOI The above composite test piece 〜 ~ flammability ^ ~ 25 - self-extinguishing (non-flammable) 6 '"The flame retardant and UL-94 combustion test conditions are to burn the vertical sample 'fire source burning 1 〇 fire rating (that is, the fireproof property is V-0 > 2 〇mm high fire source, from the bottom fluff * Two - after owing to distinguish the sample with the test > v-2 > not up to standard). 5 The results obtained by the test are shown in Table 6 below. 18 201111279 No, when the content of expanded graphite reaches 30% (sample 4), the material is extinguished (LOI data is 25) and UL_94 reaches νι level, since If the content of the expanded graphite reaches 4〇% (the test piece 5 can measure the material has a flame retardant property (L0I data is 31) and 194 can reach the level of the material, can be regarded as a good fireproof material. Therefore, it is proved that the expanded graphite of the method of the present invention can effectively improve the flame retardant properties of the composite material.
綜上所述’本發明方法採取密閉的系統進行石墨的插 層反應，利用硫酸水溶液為插層劑以及硝酸水溶液為氧化 劑於加熱溫度與時間的控制了，可得到插層效果顯著且體 積膨脹效果較以習知技術製得之產品佳的膨脹型石墨，經 混摻該膨脹型石墨後之複合材料，並可有效改善材料之= 穩定性及難難，經測試後可達極高的防火等級。本穿』備 方法之環境污染少、*僅能提高反應的效率亦可減少能源 的消耗’是-種易於商業化且具有高度競爭力的方法。 惟以上所述者，僅為本發明之較佳實施例而已，當不 能以此限定本發明實施之範圍，即大凡依本發明中請二利 範圍及發明說明内容所作之簡單的等效變化與㈣，皆仍 屬本發明專利涵蓋之範圍内。 19 201111279 【圖式簡單說明】 ，圖疋—示意圖，說明裝有反應混合物的鐵氟龍容器1並 鎖緊上蓋11後，置於一高壓釜2中並密封； 圖 2 B v ί 疋入-光粉末繞射（XRD)分析圖，說明天然鱗片石墨 (a)、貫施例1之膨脹型石墨（b)及經燃燒後所形成的已膨脹 石墨（c) ’進行χ·光粉末繞射分析之結果； 圖疋光譜圖，說明天然鱗片石墨與膨脹型石墨之 吸收波峰的分佈； 疋拉又光D晋圖，s兑明天然鱗片石墨與膨脹型石墨之圖 譜分析結果； ®疋掃皓式電子顯微鏡測得之照片，說明天然鱗片石墨 (^)、經由硫酸插層過後的膨脹型石墨（b)、經燃燒過後之已 膨脹石墨（C)的表面形態； 圖6是以熱重量分析儀（TGA)測試複合材料試片丨〜5的裂 解行為所得之熱重量（TG)曲線；及 圖7是以熱重量分析儀測試複合材料試片丨〜$的裂解行 為所得之微分熱重量（DTG)曲線。 20 201111279 【主要元件符號說明】 I ...........鐵氟龍容器 2...........高壓爸 II ..........上蓋In summary, the method of the present invention adopts a closed system for intercalation reaction of graphite, and uses an aqueous solution of sulfuric acid as an intercalation agent and an aqueous solution of nitric acid as an oxidant to control the heating temperature and time, and the intercalation effect is remarkable and the volume expansion effect is obtained. Compared with the expanded graphite which is made by the prior art, the expanded graphite is blended with the expanded graphite, and can effectively improve the stability and difficulty of the material, and can reach a very high fireproof level after testing. . The method of using this method has less environmental pollution, and * can only improve the efficiency of the reaction and reduce the energy consumption. It is a method that is easy to commercialize and highly competitive. However, the above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent change between the scope of the invention and the description of the invention is (4) It is still within the scope of the patent of the present invention. 19 201111279 [Simple description of the diagram], diagram - diagram, illustrating the Teflon container 1 containing the reaction mixture and locking the upper cover 11, placed in an autoclave 2 and sealed; Figure 2 B v ί 疋 - Light powder diffraction (XRD) analysis chart illustrating natural flake graphite (a), expanded graphite (b) of Example 1, and expanded graphite (c) formed by combustion. The results of the analysis; Figure 疋 spectrum diagram, showing the distribution of the absorption peaks of natural flake graphite and expanded graphite; 疋拉光光 mapping, s=the results of the analysis of natural flake graphite and expanded graphite; ®疋疋Photographs measured by electron microscopy, showing the surface morphology of natural flake graphite (^), expanded graphite (b) after sulfuric acid intercalation, and expanded graphite (C) after combustion; Figure 6 is a thermogravimetric analysis The instrument (TGA) tests the thermal weight (TG) curve obtained by the cracking behavior of the composite test piece 丨~5; and FIG. 7 is the differential thermal weight obtained by testing the cracking behavior of the composite test piece 丨~$ by a thermogravimetric analyzer ( DTG) curve. 20 201111279 [Description of main component symbols] I ........... Teflon container 2...........High pressure dad II ..........
21twenty one
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