201228932 -六、發明說明： 【發明所屬之技術領域】 本發明係有關於-種以天然愛玉果膠分散奈米碳管 法，尤指-種採用台灣特有天然愛玉果膠aelly fig陶 料’係具有低表面張力及高黏性可有效應用於奈米碳八 【先前技術】 讀。 由於奈米碳管具有獨特的結構，極佳的機械、熱傳導 性、化性與其商長寬比之特性，使其應用極為廣泛。但因 籲米碳管之間具有微弱的凡得瓦力，所以彼此易聚集在一起且: 溶於水或有機溶劑中’造成奈米碳管在使用上無法發揮最佳的 功用，因此分散奈米碳管將是奈米碳管應用上的—大關鍵技 術。按傳統分散奈米碳管的技術，一般都是以化學性的界面活 性劑、有機溶劑為主，然而，過程中所使用的化學原料皆有毒 性’不，容易造成人員傷害，而且更會造成嚴重的環境污染。 例如目刖習知專利前案技術，有中華民國公開第2⑼？！⑼號專 鲁利申請案’其主要係利用具有共價結合的親水物質之官能化奈 米碳管’將該等奈米碳管添加至極性溶劑之水溶液中使該等 奈米碳管分散於該水溶液中，但分散過程中所使用的極性溶劑 皆有毒性且會造成環境污染。再者，中華民國專利第⑵ 號專利案’其技術係利用水為基礎溶劑，加入分散劑、穩定劑、 成膜劑與增黏劑等溶質，以及奈米碳管，其中基礎溶劑與溶質 形成低黏度水溶液，奈米碳管則懸浮於其中，形成奈米碳管懸 浮液，分散過程中所使用的溶劑皆為有機溶劑，也會會造成環 境/亏染此外目則習知中華民國專利前案技術，公告第1258789 201228932 號與第1284116號，及/乂 p弓赞 開第200700312號與第200710029號等 專利前案，其專利技術料無針對使用天然愛玉果膠當分散 劑，及規範分散單壁奈米碳管方法。顯然，本發明為最新的分 散奈米碳管技^，而且不會對人員造成傷害及環境的污染。 有鑑於目刚現有奈米碳管分散技術仍存在缺點，本發明人 基於豐富的學識與經驗，乃積極努力投入研究，經潛心研發， 終於發展出確具進步性及產業利用性之本發明。本發明所使用 之無毒性的天然植物愛玉果膠，為台灣現特有農產品愛玉束 在台灣是-種廣受歡迎之夏日飲品，其主要成分是由愛玉瘦果 (achenes)之外果皮(pericarp)所溶離之高酯化度果膠受到果膠溶 出之内生性（endogenous)果膠酯（pectinesterase, PE)作用而生成 低酯化度果膠’再與水中之二價陽離子如：鈣、鎂等離子形成 架橋連結成網狀結構而成膠。由於本發明人觀察到愛玉果膠具 有低表面張力與高黏性等特性，果膠溶解後，經過超音波震盪， 有助於愛玉果膠能進入單壁奈米碳管的管壁末端及表面，並吸 •附於單壁奈米碳管表面，造成單壁奈米碳管間的凡得瓦爾力下 降，有效的分散單壁奈米碳管，以避免團聚現象再現。 【發明内容】 本發明之主要目的，在於提供一種製造簡便、無污染性， 可有效分散奈米碳管於水溶液中，充份發揮奈米碳管之效能的 製造方法。其技術内容，尤指一種採用台灣特有天然愛玉果膠 (jelly fig pectin)為材料’係具有低表面張力及高黏性可有效應用 於奈米碳管之分散’並利用超音波震盪進行分散處理，進一步 的降低碳管間的凡得瓦爾力。具體的技術手段流程包括有準備 4 201228932 原料、分散化處理、_、處理及烘乾處理。準備補包括備妥 -預定量的單壁奈米碳管及-預定量的純化愛玉果膠。備妥一 預定量的單壁奈米碳管，係包括純化改質：將該單壁奈米碳管 置於硫酸/賴溶液巾崎—預定時_超音波Μ ;過滤分 離：將震洗完畢之溶液以過料式將該單壁奈米碳管與該硫酸/ 硝酸溶液分離；中性化處理：以㈣子水洗掉殘留在該單壁奈 米碳管上的該硫酸/硝酸溶液，直至單壁奈米碳管的pH值維持 在中性；及供乾處理：將經中性化處理過的該單壁夺米碳與以 -預定溫度及-預定時間烘烤，以去除其上的水I備二 定量的純化愛玉果膠，係包括稀釋處理：取一 的愛玉果膠，以去離子水稀釋；及攪拌：進 ’’屯化後 拌使該愛玉果膠均勻溶於該去離子水中， 疋時間的擾 液。分散化處理:將備妥之該單壁奈米碳管二::::: 2溶液Γ利用超音波震盪i定時間，使單 勻刀散於&玉果膠水溶液中。過祕理·· ’、： 去該愛玉果膠水溶液中❹餘愛玉果膠與去=過濾、裝置渡 理：將剩餘的單壁奈米碳f以—預定溫度—烘乾處 去除多餘水It，獲得分散處理後的料衫㈣時間’以 【實施方式】 s 宜•本發明之基本技術特徵 如圖1所示，本發明以天然愛玉果 法，係包括： 砂刀政奈米碳管之方 0)準備原料，其包括： (al)備妥一預定量的單壁奈米碳管；及 201228932 (a2)備妥一預定量的純化愛玉果膠，其包括： (b)分散化處理：隨後秤取適量純化改質過之單壁奈米碳管 加入愛玉果膠水溶液中，使單壁奈米碳管均勻分散於愛玉果膠 水溶液中； (c) 過濾處理：利用抽氣過濾裝置濾去多餘的愛玉果膠；及 (d) 烘乾處理：最後將剩餘的單壁奈米碳管置於真空烘箱内 烘烤，進而得到分散處理後的單壁奈米碳管。 貳·本發明之實驗例 如圖1所示，本發明以天然愛玉果膠分散奈米碳管之方 法’係包括： (a)準備原料，其包括： (al)備妥一預定量的單壁奈米碳管，其包括： (all)純化改質：由於單壁奈米碳管本身具有雜質，必201228932 - VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for dispersing a carbon nanotube by natural jade pectin, and more particularly, a type of natural jade pectin aelly fig ceramic 'The system has low surface tension and high viscosity and can be effectively applied to nano carbon eight [previous technology] reading. Due to its unique structure, the carbon nanotubes have excellent mechanical, thermal conductivity, chemical properties and their commercial length to width ratio, making them extremely versatile. However, because of the weak van der Waals force between the carbon nanotubes, they are easy to get together and are: dissolved in water or organic solvents, which causes the carbon nanotubes to not perform optimally in use, so The carbon nanotubes will be the key technology for the application of carbon nanotubes. According to the traditional technology of dispersing carbon nanotubes, chemical surfactants and organic solvents are generally used. However, the chemical materials used in the process are all toxic, and are not likely to cause personal injury, but also cause Severe environmental pollution. For example, seeing the patented patent technology, is the Republic of China open to the second (9)? ! (9) The application for the Luli application is mainly based on the use of functionalized carbon nanotubes with covalently bonded hydrophilic materials to add the carbon nanotubes to an aqueous solution of a polar solvent to disperse the carbon nanotubes. The polar solvent used in the aqueous solution, but used in the dispersion process, is toxic and causes environmental pollution. Furthermore, the Patent No. (2) of the Republic of China Patent 'the technology uses water as a base solvent, adding a solute such as a dispersant, a stabilizer, a film former and a tackifier, and a carbon nanotube in which a base solvent and a solute are formed. A low-viscosity aqueous solution, in which a carbon nanotube is suspended, forms a carbon nanotube suspension, and the solvent used in the dispersion process is an organic solvent, which also causes environmental/loss dyeing. Moreover, it is known before the Republic of China patent. Case technology, Announcement Nos. 1258789 201228932 and No. 1284116, and /乂p Gong Zankai No. 200700312 and No. 200710029, etc., the patented materials are not targeted to use natural jade pectin as a dispersant, and specifications Dispersion of single-walled carbon nanotubes. Obviously, the present invention is the latest in dispersing carbon nanotube technology and does not cause harm to personnel and environmental pollution. In view of the shortcomings of the existing carbon nanotube dispersion technology, the present inventors have actively invested in research based on rich knowledge and experience, and have developed the present invention which is progressive and industrially usable. The non-toxic natural plant love jade pectin used in the present invention is a unique summer drink in Taiwan. It is a popular summer drink in Taiwan, and its main component is the peel of amethyth achenes. (pericarp) high esterification degree pectin dissolved by pectin ester endogenous pectin esterase (PE) to form a low esterification degree pectin' and then divalent cations in water such as: calcium The magnesium plasma forms a bridge and is connected into a mesh structure to form a glue. Since the present inventors have observed that the jade pectin has low surface tension and high viscosity, after the pectin is dissolved, the ultrasonic wave oscillates, which helps the jade pectin to enter the end of the wall of the single-walled carbon nanotube. And the surface, and suction • attached to the surface of the single-walled carbon nanotubes, resulting in a decline in the van der Waals force between the single-walled carbon nanotubes, effectively dispersing the single-walled carbon nanotubes to avoid the reunion phenomenon. SUMMARY OF THE INVENTION The main object of the present invention is to provide a manufacturing method which is easy to manufacture and non-polluting, and can effectively disperse a carbon nanotube in an aqueous solution to fully exert the performance of a carbon nanotube. Its technical content, especially the use of Taiwan's unique jadely pectin as a material with low surface tension and high viscosity, can be effectively applied to the dispersion of carbon nanotubes and dispersed by ultrasonic vibration. Treatment, further reducing the Van der Waals force between the carbon tubes. The specific technical means process includes preparation 4 201228932 raw materials, decentralized treatment, _, treatment and drying treatment. Preparations include a ready-to-predetermined amount of single-walled carbon nanotubes and a predetermined amount of purified Ai Pectin. Prepare a predetermined amount of single-walled carbon nanotubes, including purification and modification: the single-walled carbon nanotubes are placed in the sulfuric acid/lying solution, and the predetermined time is _ ultrasonic Μ; filtration separation: the shock is completed The solution is separated from the sulfuric acid/nitric acid solution by an over-feeding method; neutralization treatment: washing the sulfuric acid/nitric acid solution remaining on the single-walled carbon nanotubes with (4) water, until The pH of the single-walled carbon nanotube is maintained at neutral; and for dry treatment: the neutralized treated single-walled carbon is baked at a predetermined temperature and for a predetermined time to remove Water I prepared a second quantitative purification of jade pectin, including dilution treatment: take one of the jade pectin, diluted with deionized water; and stir: into the ''屯化, mix the love jade pectin evenly soluble The deionized water, turbulent time turbulence. Dispersion treatment: The single-walled carbon nanotubes 2::::: 2 solution will be prepared by ultrasonic vibration for a certain time, so that the single-knife is dispersed in the & jade pectin aqueous solution. After the secrets ·· ',: Go to the Ai Yu pectin aqueous solution in the Yu Ai Yu pectin and go = filtration, device treatment: the remaining single-walled nano carbon f to - predetermined temperature - drying to remove excess Water It, obtaining the shirt after the dispersion treatment (four) time 'by the embodiment' s yi · The basic technical features of the present invention are shown in Fig. 1, the present invention is based on the natural love jade fruit method, including: sand knife Zheng Nai The carbon tube side is 0) preparing raw materials, which comprise: (al) preparing a predetermined amount of single-walled carbon nanotubes; and 201228932 (a2) preparing a predetermined amount of purified ai pectin comprising: Decentralized treatment: Then, an appropriate amount of purified and modified single-walled carbon nanotubes is added to the aqueous solution of Aiyu Pectin to uniformly disperse the single-walled carbon nanotubes in the aqueous solution of Aiyu Pectin; (c) Filtration treatment : filtering out excess jade pectin by using a suction filter device; and (d) drying treatment: finally, the remaining single-walled carbon nanotubes are baked in a vacuum oven to obtain a dispersed single-walled naphthalene Carbon tube.贰·Experiment of the present invention, as shown in FIG. 1 , the method of the present invention for dispersing a carbon nanotube by natural jade pectin includes: (a) preparing a raw material comprising: (al) preparing a predetermined amount of a single Wall-nanocarbon tube, which includes: (all) purification and modification: since the single-walled carbon nanotube itself has impurities, it must
肩將單壁奈米碳管進行純化改質處理，即先將單壁奈米碳管置 於s有體積比為3 : 1的硫酸/硝酸溶液（硫酸%，硝酸中 進行超音波震請配合參賴件—所示），震㈣間為丨小時； 刀、雕：再將嚴洗完畢之溶液以過濾方式將 壁奈米碳管與硫酸/硝酸溶液分離； ㈤)巾性化處理：接著再財離子水洗掉殘留在單 :=管上的硫_肖酸溶液，直至單壁奈米碳管的pH 在中性（pH值約為7 ); 於約l00〇c的真★忸〜’’㈣理的單壁奈米碳管 1 ，烤約24小時，以去除其上的水氣； (a2)備女預定量的純化愛玉果膠，其包括· 201228932 (a21)稀釋處理：秤取一預定量之純化後的愛玉果膠， 以去離子水稀釋；及 (a22)授拌：即利用磁石攪拌機授拌約1小時，以便愛 玉果膠能均勻溶於去離子水中； (b) 分散化處理：隨後秤取適量純化改質過之單壁奈米碳管 加入愛玉果膠水溶液中，利用超音波震盈約1小時使單壁奈米 碳管均勻分散於愛玉果膠水溶液中； (c) 過濾處理：利用抽氣過濾裝置濾去多餘的愛玉果膠與去 離子水；及 (d)烘乾處理：最後將剩餘的單壁奈米碳管置於約1〇〇〇c真空烘 箱内烘烤約24小時以去除多餘的水氣，進而得到分散處理後的 單壁奈米碳管。 爹•本發明之貫驗分析 本發明係利用穿透式電子顯微鏡分析，其可作為判斷單壁 不米碳管分佈情形的卫具。附件二圖i⑻所示為單壁奈米碳管 在未經愛玉果膠處理前之結構情形，整體管徑範圍分佈較= 可看出單壁奈米碳管分散性不佳，具制結心之現象，造 =碳管在使壯餘發揮最㈣作用情件二圖i(b)所示為 團t的單壁奈♦碳管經超音波歷分散及愛 獨型式存在的證據之TEM則。 膠^覆下成单 本發明實驗例中，證明單壁奈米碳管經由超音波震盪及愛 =膠雙重分散作用下確實能降低奈米碳管叫凡得瓦爾力， 2團聚現象之功效H圖1⑻為單壁奈米碳管於水溶液 以超音波震蘯1小時，並於室溫下放置2小時後之情形。 201228932 由照片中可明顯看出下層的單壁奈米碳管因彼此糾結與纏 造成團聚沉殿現象而出現分層。而純化後之單㈣米碳管在 同條件下加人愛玉果膠分散之水溶液經超音波震盡丨 室溫下放置超過6個月，如附件三圖賴示，仍然保持稃定 均勻分散的黑色懸浮液。 以上所述’僅為本創作之一可行實施例，並非用以限定本 創作之專職圍，凡舉依據下列請求賴狀内容、特 其精神而為之其他變化料效實施，皆應包含於本創作 範圍内。本創作除上述優點外，並深具產#之利用性 改备習用所產生之缺失，而且所具體界定於請求項之特徵 見於同類物品，故而具實用性與進步性，已符合新型專利要 爰依法具文提出巾請，謹請鈞局紐㈣專利 申 請人合法之權益。 呀邊本申 【圖式簡單說明】 圖1為本發明之流程示意圖。 附件一 ··為本發明之實驗裝置圖。 附件二： 圖 壁奈米碳管 圖Ka)為未經愛玉果膠處理的單壁奈米碳管；及 為她_询_及愛玉輪覆下的單 附件三： 米碳!，液’於室溫下放置超過6個月照片：及 b)為本發明添加愛玉果膠後經超音波震盪1小時 於 201228932 室溫下放置超過6個月。 【主要元件符號說明】 (a)準備原料 （al)備妥一預定量的單壁奈米碳管 (all)純化改質 （al2)過濾分離 (al3)中性化處理 （al4)烘乾處理 (a2)備妥一預定量的純化愛玉果膠 (a21)稀釋處理 （a22)攪拌 (b)分散化處理 (d)烘乾處理 (c)過濾處理The single-walled carbon nanotubes are purified and modified by the shoulder, that is, the single-walled carbon nanotubes are first placed in a sulfuric acid/nitric acid solution (sulphuric acid%, nitric acid) with a volume ratio of 3:1. Participate in the parts - shown), between the earthquakes (four) is 丨 hours; Knife, carving: the solution is washed carefully to separate the wall carbon nanotubes from the sulfuric acid / nitric acid solution; (5)) towel treatment: then Replenish the residual water in the single: = sulfur _ _ acid solution on the tube until the pH of the single-walled carbon nanotubes is neutral (pH is about 7); at about l00 〇 c true ★ 忸 ~ ''(4) rational single-walled carbon nanotubes 1 , baked for about 24 hours to remove the moisture on it; (a2) Prepare a predetermined amount of purified Ai pectin, including 201228732 (a21) dilution treatment: Weighing a predetermined amount of purified Aiyu Pectin, diluted with deionized water; and (a22) mixing: using a magnet mixer for about 1 hour, so that the jade pectin can be uniformly dissolved in deionized water; (b) Dispersion treatment: then weigh the appropriate amount of purified and modified single-walled carbon nanotubes into the aqueous solution of Ai Jade, using ultrasonic wave 1 hour to uniformly disperse the single-walled carbon nanotubes in the aqueous solution of Aiyu Pectin; (c) Filtration treatment: filtering out excess jade pectin and deionized water by suction filtration device; and (d) drying treatment Finally, the remaining single-walled carbon nanotubes were baked in a vacuum oven of about 1 〇〇〇c for about 24 hours to remove excess moisture, thereby obtaining a single-walled carbon nanotube after dispersion treatment.爹•Perspective Analysis of the Invention The present invention utilizes a transmission electron microscope analysis, which can be used as a fixture for judging the distribution of single-walled carbon nanotubes. Figure II(8) of Annex II shows the structure of a single-walled carbon nanotube before it is treated with Aiyu Pectin. The distribution of the overall pipe diameter is better than that of the single-walled carbon nanotube. The phenomenon of the heart, the creation of the carbon tube in the exercise of the most (four) role of the situation, the second figure i (b) shows the TEM of the single-walled n-carbon tube of the group t through the ultrasonic dispersion and the existence of the unique type of evidence then. In the experimental example of the invention, it is proved that the single-walled carbon nanotubes can reduce the carbon nanotubes by the ultrasonic vibration and the dual dispersion of the love rubber. Fig. 1 (8) shows the case where a single-walled carbon nanotube was shaken in an aqueous solution for 1 hour with an ultrasonic wave and left at room temperature for 2 hours. 201228932 It is evident from the photograph that the single-walled carbon nanotubes in the lower layer are stratified due to the entanglement and entanglement of each other. The purified single (four) meter carbon tube is placed under the same conditions and added to the aqueous solution of the jade pectin dispersion. The ultrasonic solution is shaken at room temperature for more than 6 months, as shown in the attached figure, and remains uniformly dispersed. Black suspension. The above-mentioned 'is only one of the feasible examples of this creation, and is not intended to limit the full-time division of this creation. Any other changes that are based on the following requests and special effects should be included in this Within the scope of creation. In addition to the above-mentioned advantages, this creation is deeply lacking in the use of the production change, and the characteristics defined in the request item are found in similar items, so it is practical and progressive, and has met the requirements of the new patent. I have to file a lawsuit in accordance with the law. I would like to ask the Bureau of the New Zealand (4) legal rights of the patent applicant.呀本本申 [Simplified illustration of the drawings] Figure 1 is a schematic flow chart of the present invention. Annex I ·· is the experimental device diagram of the present invention. Attachment 2: Figure 4 is a single-walled carbon nanotube that has not been treated with jade pectin; and for her _ and _ _ _ _ _ _ _ _ _ _ _ _ _ _ 'Place at room temperature for more than 6 months Photo: and b) Add the jade pectin to the present invention and then subject to ultrasonic shock for 1 hour at room temperature of 201228932 for more than 6 months. [Explanation of main component symbols] (a) Preparation of raw materials (al) Preparation of a predetermined amount of single-walled carbon nanotubes (all) Purification and upgrading (al2) Filtration separation (al3) Neutralization treatment (al4) drying treatment (a2) Prepare a predetermined amount of purified Ai pectin (a21) dilution treatment (a22) agitation (b) decentralization treatment (d) drying treatment (c) filtration treatment