201202129 六、發明說明： 【發明所屬之技術領域】 剛 本發明係有關於—種改質奈米碳管之方法，尤指一 種利用超臨界二氧化碳改質奈米碳管之方法。 【先前技術】 [_ 由於奈米碳管⑽Ό本身不料任何錢基，故要 . 將高分子接^於奈米碳管上實屬難事，因此將其表面官 能基化為與高分子進行接合的先決條件。在Μ"年 、硝酸及過氧化氫 將奈米碳管氧化。至目前為止，奈米碳管表面官能基化 ㈣法大致上料五種：⑴錄化财f、⑴自由基 聚合改質、（3)界面活性劑改賓、⑷高分子吸附改質、 (5)PLV方式成長改質。 1998年SmaUey率先提出將單層壁的奈米碳管於蛾 酸/硫酸溶液進行超音波震盪，並將反應後的奈米碳管利 用過氧化氫/硫酸加熱。由其結果得知碳管被切斷成長度 〇 卿―綱⑽’兩端皆開口的短管。主因由於化學氣相沈 積方式所生產的奈米破管在管壁±，介 之五環及七環所組成的區域__ 一 hep=^ 胺化鍵結。 表單編號A0101 pairs) ’存在著較大的結構應力，同時管壁上也有⑶及 CH 2之顧產生，可透過濃额及雜等料化劑進行 破壞使’、產生氣化後的官能基。Hadd〇n則將先前所合成 出之碳s表面缓酸基加以應用。氧化後的奈米碳管表面 3有C00H及C〇〇 _之官能基，經由亞硫酿氣加以氯化 會形成反應性高的醯氯基，再藉著脂肪胺的加入酿 099122101 0992038933-0 第3頁/共1〇頁 201202129201202129 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for modifying a carbon nanotube, and more particularly to a method for modifying a carbon nanotube by supercritical carbon dioxide. [Prior Art] [_ Since the carbon nanotube (10) itself does not expect any money base, it is difficult to connect the polymer to the carbon nanotube, so the surface is functionalized to be bonded to the polymer. prerequisites. The carbon nanotubes are oxidized in Μ"year, nitric acid and hydrogen peroxide. Up to now, there have been five types of surface functionalization of carbon nanotubes: (1) recording of financial assets, (1) radical polymerization, (3) surfactant modification, (4) polymer adsorption modification, (4) 5) PLV growth and upgrading. In 1998, SmaUey first proposed to ultrasonically oscillate a single-walled carbon nanotube in a moth/sulphuric acid solution, and to heat the reacted carbon nanotubes with hydrogen peroxide/sulfuric acid. From the results, it was found that the carbon tube was cut into a short tube having a length 〇 ― 纲 纲 (10)' open at both ends. The main reason is that the nanotubes produced by the chemical vapor deposition method are in the tube wall ±, and the region consisting of the five rings and the seven rings is __ a hep=^ amination bond. Form No. A0101 pairs) ' There is a large structural stress, and at the same time, there are also (3) and CH 2 on the tube wall, which can be destroyed by the concentration and the impurity agent to generate the vaporized functional group. Hadd〇n applies the previously synthesized carbon s-surface acid-base. The surface of the oxidized carbon nanotubes has functional groups of C00H and C〇〇_, which are chlorinated by the sulphurization gas to form a highly reactive fluorenyl chloride group, and then added by the addition of fatty amines. 099122101 0992038933-0 Page 3 of 1 page 201202129
Hi rsch於2001年提出以自由基與碳管表面碳碳雙鍵 進行接合的動作，藉以提高碳管表面有機官能基的個數 ，並對於結構破損的部分加以改善。在其研究中引進三 種方式達到表面有機化。 2 0 0 3年Cy r i 11 e為保持碳管表面π鍵，故嘗試以界 面活性劑非共價鍵結吸附方式，吸附於碳管之上。其研 究中以SDS(sodium dodecyl sulfate)作為單壁型碳 管之界面活性劑，期望能使碳管均勻懸浮於水溶液中。 由其實驗結果觀察得知，碳管確實會因SDS的加入而得到 良好的懸浮分散性。但因非共價鍵結之強度不如其價鍵 結，故與高分子摻混時，雖可保持奈米碳管的優良特性 ，卻因掺混時之溫度提升、高剪應力等其他因素影響， 作為奈米複合材料顯然不如共價鍵結。 有鑑於習知技術製造之碳管在有機介質中無法有效 控制其親水或親油之界面特質，本案提供一種新的改質 奈米碳管之方法。 【發明内容】 [0003] 本發明之目的，在於提供一種利用超臨界二氧化碳 改質奈米碳管之方法，其主要利用超臨界二氧化碳輔助 之方法，使高分子寡聚物充分包覆奈米碳管，達到改質 奈米碳管之目的。 為達到上述之目的，本發明提供一種利用超臨界二 氧化碳改質奈米碳管之方法，該改質奈米碳管之方法係 包含：取一奈米碳管、一單體及一起始劑至一溶劑，得 到一混合物；震盪該混合物；該混合物置於一反應槽， 099122101 並導入一超臨界二氧化碳流體進行反應；利用一清洗溶 表單編號A0101 第4頁/共10頁 0992038933-0 201202129 劑清洗該混合物；以及真空乾燥該混合物，得到一已改 質之奈米碳管。 【實施方式】 [0004] 茲為使貴審查委員對本發明之結構特徵及所達成 之功效有更進一步之瞭解與認識，謹佐以較佳之實施例 及配合詳細之說明，說明如後：In 2001, Hi rsch proposed the action of joining free radicals with carbon-carbon double bonds on the carbon nanotube surface to increase the number of organic functional groups on the carbon nanotube surface and improve the structural damage. In the study, three methods were introduced to achieve surface organicization. In 2003, Cy r i 11 e is to maintain the π bond on the surface of the carbon tube. Therefore, it is attempted to adsorb on the carbon tube by non-covalent bonding of the surfactant. In its research, SDS (sodium dodecyl sulfate) is used as a surfactant for single-walled carbon tubes, and it is desirable to uniformly suspend the carbon tubes in an aqueous solution. It is observed from the experimental results that the carbon tube does have good suspension dispersibility due to the addition of SDS. However, since the strength of the non-covalent bond is not as good as the bond of the bond, when blended with the polymer, although the excellent characteristics of the carbon nanotube can be maintained, it is affected by other factors such as temperature increase and high shear stress during blending. As a nanocomposite, it is obviously not as covalent as a bond. In view of the fact that the carbon tube manufactured by the prior art cannot effectively control the hydrophilic or lipophilic interface characteristics in an organic medium, the present invention provides a new method for modifying the carbon nanotube. SUMMARY OF THE INVENTION [0003] The object of the present invention is to provide a method for modifying a carbon nanotube by using supercritical carbon dioxide, which mainly utilizes a supercritical carbon dioxide assisted method to fully encapsulate a polymer oligomer with nano carbon. Tube, the purpose of the modified carbon nanotubes. In order to achieve the above object, the present invention provides a method for modifying a carbon nanotube by using a supercritical carbon dioxide. The method for modifying a carbon nanotube comprises: taking a carbon nanotube, a monomer and a starter to a solvent to obtain a mixture; shaking the mixture; the mixture is placed in a reaction tank, 099122101 and introduced into a supercritical carbon dioxide fluid for reaction; using a cleaning solution form number A0101, page 4 / 10 pages 0992038933-0 201202129 cleaning agent The mixture; and vacuum drying the mixture to obtain a modified carbon nanotube. [Embodiment] [0004] For a better understanding and understanding of the structural features and the achievable effects of the present invention, the preferred embodiment and the detailed description are as follows:
請參閱第一圖，係本發明之一較佳實施例之流程示 意圖。如圖所示，本實施例提供一種利用超臨界二氧化 碳改質奈米碳管之方法，其主要利用自由基反應合成方 式，將具有碳碳雙鍵之單體接枝到奈米碳管上，更使用 超臨界二氧化碳輔助之方法，使高分子寡聚物充分包覆 奈米碳管，達到改質奈米碳管之功效。 本實施例之改質奈米碳管之方法係先執行步驟S10， 取一奈米碳管、一單體及一起始劑至一溶劑，均勻混合 奈米碳管、單體、起始劑及溶劑得到一混合物。其中奈 米碳管之型態為單壁、雙壁或多壁。單體係選自順丁烯 二Sf(Maleic anhydride, MA)及乙稀基三甲氧石圭院 (Vinyl trimethoxy silane, VTMOS)中擇其一者。 起始劑係選自過氧苯醢（Benzoyl peroxide, BP0)及偶 氮二異丁（Azobis isobutyronitrile，AIBN)中擇其 一者。溶劑係選自二甲基甲酰胺及丙酮中擇其一者。 執行步驟S10後，執行步驟S12，利用超音波震盪混 合物，主要使奈米碳管均勻分散於溶劑中。接著執行步 驟S14，混合物置於一反應槽，並導入一超臨界二氧化碳 流體進行反應，其中超臨界二氧化碳流體之形成主要為 將一二氧化碳氣體通入反應槽，提升反應槽内之壓力， 099122101 表單編號A0101 第5頁/共10頁 0992038933-0 201202129 使二氧化碳氣體轉換成超臨界二氧化碳流體，反應槽内 之壓力係介於llOOpsi與3000psi之間。而反應槽外之溫 度係介於攝氏60度與攝氏75度之間。混合物與超臨界二 氧化碳流體之反應時間係介於2小時與3小時之間。 本實施例使用超臨界二氧化碳流體主要因為二氧化 碳在氣體狀態下不具萃取能力，但當二氧化碳進入超臨 界狀態後，二氧化碳變成親有機性，因而具有溶解有機 物的能力，控制反應槽外之温度及反應槽内之壓力，讓 起始劑在超臨界狀態進行奈米碳管之表面改質。而不同 的反應槽之溫度及反應槽内之壓力下，奈米碳管之表面 改質會呈現出不同接枝之型態。然後執行步驟S16，利用 一清洗溶劑清洗混合物，其中清洗溶劑為丙酮，最後執 行步驟S18，真空乾燥混合物，得到一已改質之奈米碳管 ，真空乾燥混合物係將混合物置入烘箱中，並以攝氏60 度之溫度乾燥混合物，乾燥時間為24小時。 由上述可知，本發明所提供之利用超臨界二氧化碳 改質奈米碳管之方法，本發明主要利用超臨界二氧化碳 輔助之方法，使高分子寡聚物充分包覆奈米碳管，達到 改質奈米碳管之目的。 綜上所述，本發明係實為一具有新穎性、進步性及 可供產業利用者，應符合我國專利法所規定之專利申請 要件無疑，爰依法提出發明專利申請，祈鈞局早曰賜 准專利，至感為禱。惟，以上所述者，僅為本發明之一 較佳實施例而已，並非用來限定本發明實施之範圍，舉 凡依本發明申請專利範圍所述之形狀、構造、特徵及精 神所為之均等變化與修飾，均應包括於本發明之申請專 099122101 表單編號A0101 第6頁/共10頁 0992038933-0 201202129 利範圍内。 【圖式簡單說明】 [0005] 第一圖：本發明之一較佳實施例之流程圖。 【主要元件符號說明】 [0006] 無Please refer to the first figure, which is a schematic illustration of a preferred embodiment of the invention. As shown in the figure, the present embodiment provides a method for modifying a carbon nanotube by using supercritical carbon dioxide, which mainly uses a radical reaction synthesis method to graft a monomer having a carbon-carbon double bond to a carbon nanotube. The method of supercritical carbon dioxide assisted is further used to fully coat the carbon nanotubes with the polymer oligomer to achieve the effect of modifying the carbon nanotubes. The method for modifying the modified carbon nanotube of the embodiment first performs step S10, taking a carbon nanotube, a monomer and an initiator to a solvent, uniformly mixing the carbon nanotube, the monomer, the initiator and The solvent gave a mixture. Among them, the shape of the carbon nanotubes is single-walled, double-walled or multi-walled. The single system is selected from the group consisting of maleic anhydride (MA) and Vinyl trimethoxy silane (VTMOS). The initiator is selected from the group consisting of Benzoyl peroxide (BP0) and Azobis isobutyronitrile (AIBN). The solvent is selected from the group consisting of dimethylformamide and acetone. After step S10 is performed, step S12 is performed to ultrasonically oscillate the mixture, and the carbon nanotubes are mainly dispersed uniformly in the solvent. Next, in step S14, the mixture is placed in a reaction tank, and a supercritical carbon dioxide fluid is introduced to carry out the reaction, wherein the supercritical carbon dioxide fluid is formed mainly by introducing a carbon dioxide gas into the reaction tank to raise the pressure in the reaction tank, 099122101 A0101 Page 5 of 10 0992038933-0 201202129 Converting carbon dioxide gas into supercritical carbon dioxide fluid, the pressure in the reaction tank is between llOOpsi and 3000psi. The temperature outside the reaction tank is between 60 degrees Celsius and 75 degrees Celsius. The reaction time of the mixture with the supercritical carbon dioxide fluid is between 2 hours and 3 hours. The supercritical carbon dioxide fluid used in this embodiment is mainly because carbon dioxide does not have the extraction ability under the gas state, but when the carbon dioxide enters the supercritical state, the carbon dioxide becomes hydrophilic, thus having the ability to dissolve organic matter, controlling the temperature outside the reaction tank and the reaction tank. The pressure inside allows the initiator to undergo surface modification of the carbon nanotubes in a supercritical state. Under the different reaction tank temperatures and the pressure in the reaction tank, the surface modification of the carbon nanotubes will exhibit different grafting patterns. Then, in step S16, the mixture is washed with a cleaning solvent, wherein the cleaning solvent is acetone, and finally step S18 is performed, the mixture is vacuum dried to obtain a modified carbon nanotube, and the mixture is vacuum dried to place the mixture in an oven. The mixture was dried at a temperature of 60 ° C and the drying time was 24 hours. It can be seen from the above that the method for utilizing supercritical carbon dioxide modified carbon nanotubes provided by the present invention mainly utilizes a supercritical carbon dioxide assisting method to fully coat a carbon nanotube with a polymer oligomer to achieve upgrading. The purpose of the carbon nanotubes. In summary, the present invention is a novelty, progressive and available for industrial use, and should conform to the patent application requirements stipulated in the Patent Law of China, and the invention patent application is filed according to law. Quasi-patent, to the feeling of prayer. However, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and the shapes, structures, features, and spirits described in the claims are equally varied. And the modification should be included in the application of the present invention 099122101 Form No. A0101 Page 6 / Total 10 Page 0992038933-0 201202129. BRIEF DESCRIPTION OF THE DRAWINGS [0005] First Embodiment: A flow chart of a preferred embodiment of the present invention. [Main component symbol description] [0006] None
099122101 表單編號A0101 第7頁/共10頁 0992038933-0099122101 Form No. A0101 Page 7 of 10 0992038933-0