TWI385119B - Method for functionalizing nano-carbon material - Google Patents
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本發明係有關於一種官能化奈米碳材的方法。The present invention is directed to a method of functionalizing a nanocarbon material.
奈米碳管自1991年由Ijima發現以來即因其獨特的物理化學性質，在各應用領域極具發展潛力，諸如電磁波遮蔽與靜電消散之導電添加應用、儲能元件(如鋰二次電池、超高電容器及燃料電池等)電極、吸附材、觸媒載體及導熱材料等，皆是最關鍵的核心材料之一，預期將有數十億元的產業規模。奈米碳管/碳纖表面為六角碳環所構成，表面極少有官能基，因此其表面化學與一般熟知的氧化物有極大的差異，因此如何有效分散去團聚且可具有工業化大量改質的系統技術為奈米碳管在高分子應用的技術關鍵點。Since its discovery by Ijima in 1991, the carbon nanotubes have developed potential in various applications due to their unique physical and chemical properties, such as electromagnetic wave shielding and static dissipation, conductive energy storage applications, energy storage components (such as lithium secondary batteries, Ultra-high capacitors and fuel cells, etc.) Electrodes, adsorbent materials, catalyst carriers and thermal materials are among the most critical core materials. It is expected to have an industrial scale of several billion yuan. The surface of the carbon nanotube/carbon fiber is composed of a hexagonal carbon ring, and the surface has few functional groups. Therefore, the surface chemistry is greatly different from the well-known oxides, so how to effectively disperse and deagglomerate and have a large number of industrially modified systems Technology is a key point in the technology of nanocarbon tubes for polymer applications.
基於奈米碳纖/碳管的表面為鈍性的石墨層結構，為改善奈米碳材於溶劑或高分子樹脂中的分散性，須對奈米碳材進行表面官能化反應。目前最普遍將奈米碳材裁短或官能化的方法主要採用大量強酸(例如硫酸或硝酸)以高溫迴流或超音波處理，此類方法雖能將奈米碳管切斷，且處理後的碳管在水中具有分散性，但其缺點為製程廢酸多、碳管收率低、固液分離困難且碳管表面破壞嚴重，因此無法在工業上大量應用。如美國專利第6875412號所揭示的以氟化方式進行奈米碳管表面官能化，可再行有機置換反應以形成適當的官能基，但缺點是處理過程所需要使用的 氟氣具高毒性，而使其操作不易且對環境有害。在美國專利第6872681號及美國專利第7125533號中所揭示利用有機或無機過氧化物改質奈米碳管，是先產生自由基而攻擊碳管表面以進行官能化，然而，改質過程中仍會搭配酸液或是有機溶劑。美國專利第6531513號是利用含長碳鏈的有機胺和碳管反應，以使碳管分散在諸多有機溶劑中，但此方法有反應時間過長、處理量小、且須使用大量有機溶劑清洗之問題。又美國專利第7122165號揭示在甲醇相中，以介於約－95℃至－50℃的低溫環境下，對臭氧進行表面改質，後續再以不同氧化或還原劑調整表面官能基型態，然而除低溫環境操作不易外，仍面臨大量使用有機溶液之環保問題。The surface of the nano carbon fiber/carbon tube is a passive graphite layer structure. In order to improve the dispersibility of the nano carbon material in a solvent or a polymer resin, a surface functionalization reaction of the nano carbon material is required. At present, the most common method for cutting or functionalizing nano carbon materials is to use a large amount of strong acid (such as sulfuric acid or nitric acid) to treat at high temperature or ultrasonic wave. This method can cut the carbon nanotubes and treat them. The carbon tube has dispersibility in water, but its disadvantage is that the process waste acid is large, the carbon tube yield is low, the solid-liquid separation is difficult, and the carbon tube surface is seriously damaged, so it cannot be widely applied in industry. The surface functionalization of the carbon nanotubes in a fluorinated manner as disclosed in U.S. Patent No. 6,854,412 can be followed by an organic displacement reaction to form suitable functional groups, but the disadvantages are those required for the treatment process. Fluorine gas is highly toxic, making it difficult to handle and harmful to the environment. U.S. Patent No. 6,872, 261, and U.S. Patent No. 7,125, 533 disclose the use of organic or inorganic peroxide-modified carbon nanotubes to generate free radicals and attack the surface of the carbon nanotubes for functionalization. However, during the upgrading process, Still with acid or organic solvents. U.S. Patent No. 6531513 utilizes an organic amine having a long carbon chain and a carbon tube to react the carbon tube in a plurality of organic solvents, but the method has a long reaction time, a small amount of treatment, and must be cleaned with a large amount of organic solvent. The problem. U.S. Patent No. 7,122,165 discloses the surface modification of ozone in a methanol phase at a low temperature of about -95 ° C to -50 ° C, followed by adjustment of surface functional groups with different oxidation or reducing agents. However, in addition to the low temperature environment, it is still difficult to operate, and it still faces a lot of environmental problems in using organic solutions.
因此有需要提供一種奈米碳管/碳纖的改質方法，以克服先前技藝之不足。It is therefore desirable to provide a modification of the carbon nanotube/carbon fiber to overcome the deficiencies of the prior art.
本發明提供一種官能化奈米碳材的方法，包括：將一奈米碳材暴露於一含臭氧的氣相環境中以形成一第一官能化的奈米碳材；以及將一矽烷化合物與該第一官能化的奈米碳材進行衍生化反應，以形成一第二官能化的奈米碳材。The present invention provides a method of functionalizing a nanocarbon material, comprising: exposing a nano carbon material to an ozone-containing gas phase environment to form a first functionalized nanocarbon material; and treating the monodecane compound with The first functionalized nanocarbon material is subjected to a derivatization reaction to form a second functionalized nanocarbon material.
本發明揭示一種官能化奈米碳纖/碳管的方法，能使奈米碳纖/碳管易分散於水、有機溶劑或高分子樹脂中。適用於本發明之奈米碳纖/碳管的直徑約為(1~200)nm。奈米碳 纖/碳管，可利用例如中華民國專利案號第200640783號所揭露的漂流觸媒法，或由化學氣相沉積法、雷射蒸鍍法、電弧放電法等方法製備。在本發明之製備方法中，首先將奈米碳纖/碳管暴露於含臭氧的氣相環境中，使臭氧攻擊奈米碳纖/碳管表面的碳－碳雙鍵並進行1,3雙極環化加成反應(1,3－dipolar cycloaddition)，以形成一第一官能化的奈米碳纖/碳管。第一官能化的奈米碳纖/碳管表面的官能基末端可具有環氧基(epoxide)或羰基(carbonyl)。亦可藉由調整含臭氧的氣相環境的氣氛，例如加入具還原或氧化能力的成分，使第一官能化的奈米碳纖/碳管表面的官能基末端具有OH或COOH基。The invention discloses a method for functionalizing a nano carbon fiber/carbon tube, which enables the nano carbon fiber/carbon tube to be easily dispersed in water, an organic solvent or a polymer resin. The nano carbon fiber/carbon tube suitable for use in the present invention has a diameter of about (1 to 200) nm. Nano carbon The fiber/carbon tube can be prepared by a drifting catalyst method as disclosed in, for example, the Republic of China Patent No. 200640783, or by a chemical vapor deposition method, a laser evaporation method, an arc discharge method, or the like. In the preparation method of the present invention, the nano carbon fiber/carbon tube is first exposed to an ozone-containing gas phase environment, and the ozone attacks the carbon-carbon double bond on the surface of the carbon fiber/carbon tube and performs a 1,3 bipolar ring. A 1,3-dipolar cycloaddition is formed to form a first functionalized nanocarbon/carbon tube. The functional end of the surface of the first functionalized nanocarbon/carbon tube may have an epoxide or a carbonyl. The functional end of the surface of the first functionalized nanocarbon/carbon tube may also have an OH or COOH group by adjusting the atmosphere of the ozone-containing gas phase environment, for example, by adding a reducing or oxidizing component.
臭氧可經由商用臭氧產生機製造，氧氣進氣量約為0.1~10 L/min，出口臭氧的體積濃度約為0.02~20%。奈米碳纖/碳管可被置於在旋轉爐、流體化床、填充床等反應器中與臭氧進行反應。奈米碳纖/碳管與臭氧的反應的溫度是介於50℃至300℃，反應壓力是介於約0.01~1大氣壓，臭氧的體積濃度是介於0.02%至20%。具還原能力的成分包括甲醇、乙醇、乙二醇、甲醛、乙醛、乙二醛酸、聯胺。具氧化能力的成分包括水氣、雙氧水、硫酸、硝酸。具還原或氧化能力的成分的總莫耳數是為臭氧莫耳數約1至100倍。Ozone can be produced by a commercial ozone generator with an oxygen intake of about 0.1 to 10 L/min and a volume concentration of about 0.02 to 20% of the exported ozone. The nano carbon fiber/carbon tube can be placed in a reactor such as a rotary furnace, a fluidized bed, a packed bed, and the like to react with ozone. The temperature at which the carbon fiber/carbon tube reacts with ozone is between 50 ° C and 300 ° C, the reaction pressure is between about 0.01 and 1 atm, and the volume concentration of ozone is between 0.02% and 20%. Reducing components include methanol, ethanol, ethylene glycol, formaldehyde, acetaldehyde, glyoxylic acid, and hydrazine. Oxidizing components include water vapor, hydrogen peroxide, sulfuric acid, and nitric acid. The total number of moles of the reducing or oxidizing component is about 1 to 100 times the ozone molar amount.
接著將矽烷化合物與第一官能化的奈米碳纖/碳管的表面在液相或氣相環境中，較佳為氣相環境且與臭氧反應時的同址(in－situ)環境中，進行衍生化反應，以形成一第二官 能化的奈米碳纖/碳管。矽烷化物包括3－環氧丙基三甲氧基矽烷(3－glycidoxypropyl trimethoxysilane)、3－環氧丙基三乙氧基矽烷(3－glycidoxypropyl triethoxysilane)、3－環氧丙基甲基二乙氧基矽烷(3－glycidoxypropyl methyldiethoxysilane)、2－(3,4環氧基環己基)－乙基三甲氧基矽烷(2－(3,4 epoxycyclohexyl)－ethyltrimethoxysilane)、3－胺基丙基三甲氧基矽烷(3－aminopropyl trimethoxysilane)、3－胺基丙基三乙氧基矽烷(3－aminopropyl triethoxysilane)、N－2(氨乙基)3－氨丙基甲基二甲氧基矽烷(N－2(aminoethyl)3－aminopropylmethyldimethoxysilane)、N－2(氨乙基)3－氨丙基三甲氧基矽烷(N－2(aminoethyl)3－aminopropyltrimethoxysilane)、N－2(氨乙基)3－氨丙基三乙氧基矽烷(N－2(aminoethyl)3－aminopropyltriethoxysilane)、3－甲丙烯氧基丙基－甲基二甲氧基矽烷(3－methacryloxypropyl methyldimethoxysilane)、3－甲丙烯氧基丙基－三甲氧基矽烷(3－methacryloxypropyl trimethoxysilane)、3－甲丙烯氧基丙基－甲基二乙氧基矽烷(3－methacryloxypropyl methyldiethoxysilane)、3－甲丙烯氧基丙基－三乙氧基矽烷(3－methacryloxypropyl triethoxysilane)、3－丙烯氧基丙基－三甲氧基矽烷(3－acryloxypropyl trimethoxysilane)、3－異氰酸丙基三乙氧基矽烷(3－isocyanatopropyl triethoxysilane)、乙烯三甲氧基矽烷(vinyltrimethoxysilane)或乙烯基三乙氧基矽烷(vinyltriethoxysilane)。矽烷化物的末端具有特定官能基， 例如環氧基、胺基、羥基、羧基、異氰酸酯基、烯基、丙烯酸酯基、醛基、磺酸基或硫基。矽烷化合物的添加莫耳數為奈米碳材莫耳數的0.005至1倍。衍生化反應的反應溫度約為50℃至200℃，反應時間約為0.5至72小時。第二官能化的奈米碳纖/碳管末端可具有環氧基、胺基、羥基、羧基、異氰酸酯基、烯基、丙烯酸酯基、醛基、磺酸基或硫基，表面官能化的比例是介於約0.5%至約50%。The surface of the first functionalized nanocarbon/carbon tube is then subjected to a liquid or gas phase environment, preferably a gas phase environment and an in-situ environment in the reaction with ozone. Derivatization reaction to form a second official Energyized nano carbon fiber / carbon tube. The decanoate includes 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-epoxypropylmethyldiethoxysilane 3-glycidoxypropyl methyldiethoxysilane, 2-(3,4 epoxycyclohexyl)-ethyltrimethoxysilane, 3-aminopropyltrimethoxydecane (3-aminopropyl trimethoxysilane), 3-aminopropyl triethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxydecane (N-2 ( Aminoethyl)3-aminopropylmethyldimethoxysilane), N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyltri N-2 (aminoethyl 3-aminopropyltriethoxysilane), 3-methacryloxypropyl methyldimethoxysilane, 3-methacryloxypropyl-trimethoxy 3-methacryloxypropyl trimethoxysilane 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-propenyloxypropane 3-acryloxypropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, vinyltrimethoxysilane or vinyltriethoxysilane ). The end of the decanoate has a specific functional group, For example, an epoxy group, an amine group, a hydroxyl group, a carboxyl group, an isocyanate group, an alkenyl group, an acrylate group, an aldehyde group, a sulfonic acid group or a sulfur group. The molar number of moles of the decane compound is 0.005 to 1 times the number of moles of the nanocarbon material. The reaction temperature of the derivatization reaction is about 50 ° C to 200 ° C, and the reaction time is about 0.5 to 72 hours. The second functionalized carbon fiber/carbon tube end may have an epoxy group, an amine group, a hydroxyl group, a carboxyl group, an isocyanate group, an alkenyl group, an acrylate group, an aldehyde group, a sulfonic acid group or a sulfur group, and the ratio of surface functionalization It is between about 0.5% and about 50%.
因此，可依據水、有機溶劑或高分子樹脂的性質，調整奈米碳纖/碳管的表面極性及官能基型態，使奈米碳纖/碳管與水、有機溶劑或高分子樹脂之間具有親合力或鍵結力，且奈米碳纖/碳管是均勻穩定地分散於有機溶劑或高分子樹脂中。有機溶劑包括甲醇、乙醇、異丙醇(IPA)、正丁醇、異戊醇、醋酸乙酯(EAC)、醋酸丁酯(BAC)、己烷、正戊烷、丁基酣醇(BCS)、甲基酣醇(MCS)丙酮、丁酮、甲基異丁酮(MIBK)、乙二醇(EG)、N－甲基吡咯酮(NMP)、二甲基甲醯胺(DMF)、二甲基乙醯胺(DMAC)、四氫呋喃(THF)、甲苯或煤油。高分子樹脂包括例如尼龍(Nylon)、聚丙烯(PP)、聚對苯二甲酸二丁酯(PBT)、聚苯醚(PPO)、聚碳酸酯(PC)、丙烯腈、丁二烯、苯乙烯共聚物(ABS)、聚氯乙烯(PVC)等的熱塑性樹脂，或不飽和聚酯樹脂、環氧樹脂、酚樹脂等熱固性樹脂。高分子樹脂也包括聚乳酸(PLA)、聚氨酯(PU)、聚酯(PET)、聚醯亞胺(PI)或聚醚醚酮(PEEK)。當奈米碳纖/碳管與臭氧的反應及衍生化反應皆是在氣相環境中進行，所生成的官能化的奈米碳纖/碳管可直 接被應用，而不需再經過繁雜的純化或乾燥步驟，因此能夠簡化製程並減少生產成本。奈米碳纖/碳管改質的製程環境溫和且不會產生過多的有機廢液或酸液，因此具有較佳的操作性及工業化價值。Therefore, depending on the nature of the water, the organic solvent or the polymer resin, the surface polarity and the functional group type of the carbon fiber/carbon tube can be adjusted so that the carbon fiber/carbon tube has a water and an organic solvent or a polymer resin. Affinity or bonding force, and the nano carbon fiber/carbon tube is uniformly and stably dispersed in an organic solvent or a polymer resin. Organic solvents include methanol, ethanol, isopropanol (IPA), n-butanol, isoamyl alcohol, ethyl acetate (EAC), butyl acetate (BAC), hexane, n-pentane, butyl decyl alcohol (BCS) , methyl sterol (MCS) acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), ethylene glycol (EG), N-methylpyrrolidone (NMP), dimethylformamide (DMF), two Methylacetamide (DMAC), tetrahydrofuran (THF), toluene or kerosene. The polymer resin includes, for example, nylon (Nylon), polypropylene (PP), polybutylene terephthalate (PBT), polyphenylene ether (PPO), polycarbonate (PC), acrylonitrile, butadiene, benzene. A thermoplastic resin such as an ethylene copolymer (ABS) or polyvinyl chloride (PVC), or a thermosetting resin such as an unsaturated polyester resin, an epoxy resin or a phenol resin. The polymer resin also includes polylactic acid (PLA), polyurethane (PU), polyester (PET), polyimide (PI) or polyetheretherketone (PEEK). When the reaction between the carbon fiber/carbon tube and ozone and the derivatization reaction are carried out in a gas phase environment, the resulting functionalized nano carbon fiber/carbon tube can be straight. The application can be applied without complicated purification or drying steps, thus simplifying the process and reducing production costs. Nano carbon fiber / carbon tube modification process environment is mild and does not produce excessive organic waste liquid or acid, so it has better operability and industrial value.
本發明並不限定於奈米碳纖/碳管，還可應用於其他例如奈米碳球的奈米碳材。The present invention is not limited to nano carbon fibers/carbon tubes, and can be applied to other nano carbon materials such as nano carbon spheres.
為了讓本發明之上述和其他目的、特徵，及優點能更明顯易懂，下文特舉較佳實施例，做詳細說明如下：The above and other objects, features, and advantages of the present invention will become more apparent and understood.
取3 g奈米碳纖至於旋轉爐中，將進料速率為2 L/min、濃度為1%的臭氧通入旋轉爐中，另外以氬氣(Ar)挾帶50%的H2 O2 水溶液通入旋轉爐中，其進料速率為0.16 g/min。反應溫度為200℃，反應時間為1小時。奈米碳纖表面官能化的比例是以程溫脫附實驗，計算脫附氣體中的碳數佔碳纖表面總碳數中的比例而得。奈米碳纖表面改質比例約為21.8%。接著進行衍生官能化反應，取3g經臭氧改質的奈米碳纖置於迴流反應瓶中，加入15g水及135g異丙醇(isopropyl alcohol,IPA)，升溫至80℃，再加入0.6 g 3－(2,3－環氧丙基)丙基三乙氧基矽烷(3－(2,3－epoxypropoxy)propyl－triethoxysilane)，經迴流反應2小時，再進行過濾、清洗、乾燥的步驟，以得到官能化的奈米碳纖。取0.4 g改質後的碳纖加入20 g的N－甲基吡咯酮(N－Methyl－2－Pyrrolidone,NMP)中，使用超音波振盪器振 盪1小時後，可得到穩定的均勻碳纖分散液。Take 3 g of nano carbon fiber into the rotary furnace, and feed the ozone with a feed rate of 2 L/min and a concentration of 1% into the rotary furnace, and further bring a 50% H 2 O 2 aqueous solution with argon (Ar). It was passed through a rotary furnace at a feed rate of 0.16 g/min. The reaction temperature was 200 ° C and the reaction time was 1 hour. The ratio of surface functionalization of nanocarbon fibers is obtained by a temperature-temperature desorption experiment, and the ratio of the carbon number in the desorbed gas to the total carbon number on the surface of the carbon fiber is calculated. The surface modification ratio of nano carbon fiber is about 21.8%. Then, the derivatization functionalization reaction was carried out, and 3 g of ozone-modified nano carbon fiber was placed in a reflux reaction bottle, 15 g of water and 135 g of isopropyl alcohol (IPA) were added, and the temperature was raised to 80 ° C, and then 0.6 g of 3- 3 was added. (2,3-epoxypropyl)propyl-triethoxysilane, after refluxing for 2 hours, followed by filtration, washing, and drying to obtain Functionalized nano carbon fiber. 0.4 g of the modified carbon fiber was added to 20 g of N-methylethylpyrrolidone (NMP), and after shaking for 1 hour using an ultrasonic oscillator, a stable uniform carbon fiber dispersion was obtained.
相同於比較例1的步驟，其中是將奈米碳纖與臭氧的反應溫度改為50℃，所得到奈米碳纖的表面改質比例約為13.4%。The same procedure as in Comparative Example 1, in which the reaction temperature of the nano carbon fiber and ozone was changed to 50 ° C, the surface modification ratio of the obtained nano carbon fiber was about 13.4%.
相同於比較例1的步驟，其中是將奈米碳纖與臭氧的反應溫度改為100℃，而所得到奈米碳纖的表面改質比例約為19.2%。The same procedure as in Comparative Example 1, in which the reaction temperature of the nano carbon fiber and ozone was changed to 100 ° C, and the surface modification ratio of the obtained nano carbon fiber was about 19.2%.
相同於比較例1的步驟，其中是將奈米碳纖與臭氧的反應溫度改為150℃，而所得到奈米碳纖的表面改質比例約為21.6%。The same procedure as in Comparative Example 1, in which the reaction temperature of the nano carbon fiber and ozone was changed to 150 ° C, and the surface modification ratio of the obtained nano carbon fiber was about 21.6%.
取0.4 g未改質的碳纖加入20 g的NMP中，使用超音波振盪器振盪1小時後，碳纖是沉降於NMP的底部，並無法形成均勻的分散液。0.4 g of unmodified carbon fiber was added to 20 g of NMP, and after shaking for 1 hour using an ultrasonic oscillator, the carbon fiber settled at the bottom of the NMP, and a uniform dispersion could not be formed.
相同於比較例1的步驟，其中是在奈米碳纖與臭氧的 反應環境中不通入H2 O2 水溶液，所得到奈米碳纖的表面改質比例約為28.9%。The same procedure as in Comparative Example 1 was carried out in which the aqueous solution of H 2 O 2 was not introduced in the reaction environment of nano carbon fiber and ozone, and the surface modification ratio of the obtained nano carbon fiber was about 28.9%.
相同於比較例1的步驟，其中是在氣相環境中進行衍生官能化反應，取10g經臭氧改質的奈米碳纖置於反應瓶中，以氬氣狹帶水以及3－(2,3－環氧丙基)丙基三乙氧基矽烷，其流量分別為0.34g/min及0.048g/min，通入反應瓶中進行反應，反應溫度為125℃，反應時間為2小時，以得到官能化的奈米碳纖。取0.4 g改質後的碳纖加入20 g的N－甲基吡咯酮(N－Methyl－2－Pyrrolidone, NMP)中，使用超音波振盪器振盪1小時後，可得到穩定的均勻碳纖分散液。The same procedure as in Comparative Example 1, in which the derivatization functionalization reaction was carried out in a gas phase environment, and 10 g of ozone-modified nano carbon fiber was placed in a reaction flask with argon-clamped water and 3-(2,3). - Ethoxypropyl) propyl triethoxy decane, the flow rate of which is 0.34 g / min and 0.048 g / min, respectively, into the reaction flask for reaction, the reaction temperature is 125 ° C, the reaction time is 2 hours, to obtain Functionalized nano carbon fiber. 0.4 g of the modified carbon fiber was added to 20 g of N-methylethylpyrrolidone (NMP), and after shaking for 1 hour using an ultrasonic oscillator, a stable uniform carbon fiber dispersion was obtained.
相同於比較例1的步驟，其中是將衍生官能化反應的改質劑改為3－氨基丙基三乙氧基矽烷(3－aminopropyltrimethoxy－silane)。取0.4 g改質後的碳纖加入20 g的N－甲基吡咯酮(N－methyl－2－pyrrolidone,NMP)中，使用超音波振盪器振盪1小時後，可得到穩定的均勻碳纖分散液。The procedure is the same as in Comparative Example 1, in which the modifier for derivatization of the functionalization reaction is changed to 3-aminopropyltrimethoxy-silane. 0.4 g of the modified carbon fiber was added to 20 g of N-methyl-2-pyrrolidone (NMP), and after shaking for 1 hour using an ultrasonic oscillator, a stable uniform carbon fiber dispersion was obtained.
相同於比較例1的步驟，其中是將0.4 g改質後的碳纖加入20 g的二甲基甲醯胺(dimethyl acetamide,DMAC)中， 使用超音波振盪器振盪1小時後，可得到穩定的均勻碳纖分散液。The same procedure as in Comparative Example 1, in which 0.4 g of the modified carbon fiber was added to 20 g of dimethyl acetamide (DMAC). After shaking for 1 hour using an ultrasonic oscillator, a stable uniform carbon dispersion was obtained.
相同於比較例1的步驟，其中是將0.5g改質後的碳纖加入10g聚碳酸酯(polycarbonate,PC)中，利用微型混鍊機以270℃、100 rpm的條件進行混鍊並製成試片，以得到碳纖複合材料。碳纖複合材料的機械拉伸測試結果列於表1。從碳纖複合材料的拉伸斷面SEM圖(未顯示)可得知碳纖是均勻分散於碳纖複合材料中。The procedure of Comparative Example 1 was carried out, in which 0.5 g of the modified carbon fiber was added to 10 g of polycarbonate (PC), and the mixture was mixed at 270 ° C and 100 rpm by a micro-blender machine to prepare a test piece. To obtain a carbon fiber composite material. The mechanical tensile test results of the carbon fiber composite materials are shown in Table 1. From the SEM image of the tensile section of the carbon fiber composite material (not shown), it is known that the carbon fibers are uniformly dispersed in the carbon fiber composite material.
將0.5g未改質的碳纖加入10g的PC中，利用微型混鍊機以270℃、100 rpm的條件進行混鍊並製成試片，以得到碳纖複合材料。碳纖複合材料的機械拉伸測試結果列於表1。從碳纖複合材料的拉伸斷面SEM圖(未顯示)可得知碳纖是團聚於碳纖複合材料中，並未均勻分散於樹脂中。0.5 g of unmodified carbon fiber was placed in 10 g of PC, and mixed with a micro-blender at 270 ° C and 100 rpm to prepare a test piece to obtain a carbon fiber composite material. The mechanical tensile test results of the carbon fiber composite materials are shown in Table 1. From the SEM image of the tensile cross section of the carbon fiber composite material (not shown), it is known that the carbon fibers are agglomerated in the carbon fiber composite material and are not uniformly dispersed in the resin.
相同於實施例1的步驟，其中是將0.5g改質後的碳纖加入10g PC中，利用微型混鍊機以270℃、100 rpm的條件進行混鍊並製成試片，以得到碳纖複合材料。碳纖複合材料的機械拉伸測試結果列於表1。The procedure of Example 1 was carried out, in which 0.5 g of the modified carbon fiber was added to 10 g of PC, and mixed with a micro-blender at 270 ° C and 100 rpm to prepare a test piece to obtain a carbon fiber composite material. The mechanical tensile test results of the carbon fiber composite materials are shown in Table 1.
相同於實施例1的步驟，其中是將0.4g改質後的碳纖加入含20g環氧樹脂(EPON 828/Shell)及三乙烯四胺(TETA)的2－丁酮(MEK)溶劑中，TETA/EPON 828莫耳比為2.2：1，再以80、100、120℃的熱處理程序進行硬化。從碳纖複合材料的拉伸斷面SEM圖(未顯示)可得知奈米碳纖是均勻分散於碳纖複合材料中。The same procedure as in Example 1, in which 0.4 g of the modified carbon fiber was added to a 2-butanone (MEK) solvent containing 20 g of epoxy resin (EPON 828/Shell) and triethylenetetramine (TETA), TETA. The /EPON 828 has a molar ratio of 2.2:1 and is hardened by a heat treatment procedure of 80, 100, and 120 °C. From the SEM image of the tensile section of the carbon fiber composite material (not shown), it is known that the nano carbon fiber is uniformly dispersed in the carbon fiber composite material.
將0.4g未改質的碳纖加入含20g環氧樹脂(EPON 828)及三乙烯四胺(TETA)的2－丁酮(MEK)溶劑中，其中TETA/EPON 828莫耳比為2.2：1，再以80、100、120℃的熱處理程序進行硬化。從碳纖複合材料的拉伸斷面SEM圖(未顯示)可得知奈米碳纖是聚集為數十微米的團聚，並非均勻分散於樹脂中。0.4 g of unmodified carbon fiber was added to a 2-butanone (MEK) solvent containing 20 g of epoxy resin (EPON 828) and triethylenetetramine (TETA), wherein the TETA/EPON 828 molar ratio was 2.2:1. The curing was carried out by a heat treatment procedure of 80, 100, and 120 °C. From the SEM image (not shown) of the tensile cross section of the carbon fiber composite material, it is found that the nano carbon fibers are aggregated at a few tens of micrometers, and are not uniformly dispersed in the resin.
經過與臭氧反應及衍生反應的奈米碳材可均勻穩定地分散於有機溶劑或高分子樹脂中。表1的結果顯示，在比較例10中未改質的奈米碳材由於無法均勻分散於高分子樹脂中，因此所得到碳纖複合材料強度的增強效果小；在實施例2及比較例9中被改質的奈米碳材由於可均勻分散於高分子樹脂中，因此所得到碳纖複合材料強度的增強效果大。The nanocarbon material subjected to the reaction with ozone and the derivatization reaction can be uniformly and stably dispersed in an organic solvent or a polymer resin. The results of Table 1 show that the nanocarbon material which was not modified in Comparative Example 10 was not uniformly dispersed in the polymer resin, so that the strength of the obtained carbon fiber composite material was small, and in Example 2 and Comparative Example 9, Since the modified nano carbon material can be uniformly dispersed in the polymer resin, the strength of the obtained carbon fiber composite material is enhanced.
雖然本發明已以數個較佳實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之 精神和範圍內，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the present invention, and those skilled in the art, without departing from the invention. In the spirit and scope, the scope of protection of the present invention is defined by the scope of the appended claims.
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