1282345 成、發明說明 【發明所屬之技術領域】 顆粒的方法，特定 製備具桿狀及高傳 本發明係關於-種製備聚苯胺奈米 言之，係關於-種以低溫微乳化聚合來 導性聚苯胺奈米顆粒的方法。 L光前技術】1282345 成,发明发明 [Technical field of invention] Particle method, specific preparation with rod shape and high transmission The invention relates to the preparation of polyaniline, which is based on low temperature microemulsion polymerization. A method of polyaniline nanoparticles. L light front technology]
隨著電子及資訊產I 、▲ 、Κ屋業的快速發展，傳導性材料的應用 領域也變得更為多元化，且對以傳導性聚合物來取代 性金屬材料的研究也曰益盛"導性聚合物可被應用於 相當多領域令，例如微電磁屏障、銦錫氧化物(ιτ〇) 物、碳纖維的替代物、—種磁性記錄㈣…㈣㈣b -種發光裝置(LED)、_種锂離子電池的陰極材料 光傳輸材料等等。 當上述之傳導性《合物被製成奈米顆粒日夺，相較於傳 統大尺吋的傳導性聚合物而言，因奈米顆粒的小尺寸之 故，使得該聚合物得以表現出更多的欲求特性。奈米顆粒 係指一種體積介於一分子與一大尺寸固體間的材料而言， 且-般係介於1至10奈米間。該奈米顆粒具有與分子和/ 或一大尺寸固體不同的磁性、光學及電子特性；及奈米顆 粒專有的特性，一般將此專有特性稱為「量子大小效應 (Quantum Size Effect)」。因此，奈米顆粒有時也被稱為;: 點（quantum dot)」° 聚苯胺’代表性傳導聚合物的一種，其為一種黑色的 3 1282345With the rapid development of electronic and information products I, ▲, and Κ屋, the application of conductive materials has become more diversified, and the research on the replacement of metallic materials with conductive polymers is also beneficial. Conductive polymers can be used in a wide range of applications, such as micro-electromagnetic barriers, indium tin oxide (ITO), carbon fiber substitutes, magnetic recordings (4)... (4) (iv) b-type illuminators (LED), _ A cathode material optical transmission material of a lithium ion battery or the like. When the above-mentioned conductive "complex is made into nano-particles, compared with the conventional conductive polymer of large-sized enamel, the polymer is able to exhibit more because of the small size of the nano-particles. More desire characteristics. Nanoparticle refers to a material having a volume between one molecule and a large size solid, and is generally between 1 and 10 nanometers. The nanoparticle has different magnetic, optical and electronic properties than the molecule and/or a large size solid; and the proprietary properties of the nanoparticle, which is generally referred to as the "Quantum Size Effect". . Therefore, nanoparticle is sometimes referred to as;: quantum dot" ° polyaniline's one of the representative conductive polymers, which is a black 3 1282345
Ss. 聚合物，係苯胺單體在酸性溶液中氧化聚合後的產物，且 傳統上習稱其為「黑苯胺（aniline black)」。在1 980年代中 期發現，當將質子酸（protonic acid)摻雜入聚苯胺中時，將 可使聚苯胺的傳導性大幅升高。在該發現之後，就吸引了 不少習知技藝者專門研究聚苯胺，希望將其發展成一種欲 求的傳導性聚合物。而同時，聚苯胺及其衍生物還有其他 優點，即其容易製造、價格低廉、且具有欲求的空氣及熱 安定性。當藉由散佈聚苯胺至其他非傳導性聚合物基質中 來產生一電磁屏障時，該聚苯胺需均勻地散佈於該基質 中，且該兩材料應在不會引起兩聚合物產生相分離的情況 下，形成一均勻的複合物。如果聚苯胺奈米顆粒係用於此 一目的，則相較於一般聚苯胺微顆粒而言，聚苯胺需更均 勻地被散佈在基質中，且可形成更均勻的聚苯胺充填物/ 基質複合物。此外，隨著聚苯胺充填物的傳導性升高之際， 複合物的傳導性也會跟著升高，且可獲致更欲求的電磁屏 障。因此，亟需一種製備高傳導性聚苯胺奈米顆粒的方法。 【内容】 本發明主要目的是提供一種製備具桿狀及高傳導性聚 苯胺奈米顆粒的方法。 本發明的其他目的是提供一種以製備聚苯胺奈米顆粒 的方法，其係能大幅降低微乳化聚合過程中所需的界面活 性劑用量。 本發明的另一目的是提供一種製備聚苯胺奈米顆粒的 4 1282345Ss. A polymer which is a product of oxidative polymerization of an aniline monomer in an acidic solution and is conventionally referred to as "aniline black". It was found in the mid-1980s that when protonic acid was doped into polyaniline, the conductivity of polyaniline was greatly increased. After this discovery, many skilled artisans have been attracted to specialize in polyaniline, hoping to develop it into a desired conductive polymer. At the same time, polyaniline and its derivatives have other advantages, namely, they are easy to manufacture, inexpensive, and have desirable air and heat stability. When an electromagnetic barrier is created by dispersing polyaniline into other non-conductive polymer matrices, the polyaniline needs to be uniformly dispersed in the matrix, and the two materials should not cause phase separation of the two polymers. In this case, a homogeneous composite is formed. If polyaniline nanoparticles are used for this purpose, the polyaniline needs to be more uniformly dispersed in the matrix than the general polyaniline microparticles, and a more uniform polyaniline filling/matrix composite can be formed. Things. In addition, as the conductivity of the polyaniline filler increases, the conductivity of the composite also increases, and a more desirable electromagnetic barrier can be obtained. Therefore, there is a need for a method of preparing highly conductive polyaniline nanoparticles. [Contents] A main object of the present invention is to provide a process for preparing rod-shaped and highly conductive polyaniline nanoparticles. Another object of the present invention is to provide a process for preparing polyaniline nanoparticles which substantially reduces the amount of interfacial activator required for microemulsion polymerization. Another object of the present invention is to provide a preparation of polyaniline nanoparticles 4 1282345
方法’其係能大幅降低所需反應物的用量且本發 包含的步驟均非常簡單。 本月的另一目的為提供一種製備聚苯胺奈 方法，該聚笨胺奈米顆粒係可作為一種電子及磁 例如電磁屏障、-種磁性記錄媒體等等。 ,$達到上述這些目的，本發明提供一種以微乳 製備高傳導性聚苯胺奈米顆粒的方法，其至少包 驟：添加一種界面活性劑至一包括水及一種有機港 溶劑混合物中，並料該界面活性劑以形成 (micelle),添加苯胺單體至一内含該微胞的反應溶 一摻雜物及-氧化劑》合該苯胺單體使形力聚苯《 過里有機洛劑至該反應溶液中以將該聚苯胺與 離車又佳疋’該形成微胞的步驟係在-3〇。〇至〇。〇 溶劑混合物中的有機溶劑可選自由甲醇、乙醇、丁 癸醇及其之混合物所組成的群組中；且該有機溶受 為該溶劑混合物用量的20%至40%(重量％)。 【實施方式】 參照下列說明，將可更清楚了解本發明的優點 容。 依據本發明以極低溫微乳化聚合製備聚苯胺 的方法’其可大幅降低微乳化聚合所需界面活 1 ’並可改善所得聚苯胺奈米顆粒的傳導性及產」 為製備出本發明之聚苯胺奈米顆粒，需於低 明方法所 米顆粒的 性材料， 化聚合來 含下列步 1劑在内的 一種微胞 =液中，以 f ;並添加 該微胞分 I執行，該 醇、辛醇、 的用量係 及技術内 奈米顆粒 性劑的用 ψ ° 於o°c的 1282345 :年圮日修 溫度下添加一種界面活性劑至一反應溶劑中，較佳是於-3 0 C至-1 0 °C間的溫度下添加，更佳係於約-2 0 °C的溫度下添 加，並攪拌該反應溶液約2 0至4 0分鐘，較佳是約3 0分鍾。 在本發明中，形成微胞的步驟係於極低的溫度下進行。因 此’為了防止溶劑；東結，在形成微胞的步驟中係使用一種 包括水及有機溶劑在内的溶劑混合物。較佳的有機溶劑包 括f醇、乙醇、丁醇、辛醇、癸醇或其之混合物；且所使用 的水較佳為蒸餾水。有機溶劑與水的比例可視情況調整，只 要溶劑不會在反應溫度下凍結即可。有機溶劑的用量較佳為 該混合溶劑總量的20%至40%(重量％)間，且更佳為3〇%(重 量％)。當有機溶劑的用量低於2〇%(重量％)時，該形成微胞 步驟中的反應溫度將不夠低。當有機溶劑的用量高於4〇%(重 量％)時，將無法充分執行該形成微胞的步驟。此外，當該形 成微胞步驟的溫度係低於-3(TC時，將無法充分形成微胞。 當該形成微胞步驟的溫度係高於時，則將無法大幅降 低所需界面活性劑的用量。 該添加到溶劑混合物中的界面活性劑可以是一種陽離 子界面活性劑、一種陰離子界面活性劑及其之混合物。較 佳的陽離子界面活性劑包括演化辛基三甲基銨（〇tab)、漠 化癸基三甲基銨（DeTAB)、漠化十二烷基三曱基銨（DTAB)及 其之混合物。較佳的陰離子界面活性劑包括十二烷基硫酸鈉 (SDS)、二辛基硫代琥珀酸鈉及其之混合物。對每丨〇〇份重 量的溶劑混合物而言，界面活性劑的用量較佳係介於〇 8份 至2.5份重量間。當界面活性劑的用量低於〇·8份重量時，The method 'is capable of drastically reducing the amount of reactants required and the steps involved in the present invention are very simple. Another object of the month is to provide a process for preparing a polyaniline nanoparticle which can be used as an electronic and magnetic material such as an electromagnetic barrier, a magnetic recording medium or the like. In order to achieve the above objects, the present invention provides a method for preparing highly conductive polyaniline nanoparticles by using microemulsion, which comprises at least a step of adding a surfactant to a mixture comprising water and an organic solvent. The surfactant is formed by adding an aniline monomer to a reaction-dissolving dopant and an oxidizing agent containing the micro-cell, and the aniline monomer is used to form a polyphenylene benzoate In the reaction solution, the step of forming the microcells is carried out at -3 Torr with the step of removing the polyaniline from the vehicle. 〇 to 〇. The organic solvent in the solvent mixture may be selected from the group consisting of methanol, ethanol, butanol, and mixtures thereof; and the organic solvent is from 20% to 40% by weight based on the amount of the solvent mixture. [Embodiment] Advantages of the present invention will be more clearly understood from the following description. According to the present invention, a method for preparing polyaniline by ultra-low temperature microemulsion polymerization can greatly reduce the interface activity required for microemulsification polymerization and improve the conductivity and yield of the obtained polyaniline nanoparticle. The aniline nanoparticles are required to be polymerized in a low-light method to form a microcell=liquid in a microcell=liquid containing the following step 1; and the microcell fraction is added to perform the alcohol, The amount of octanol, and the amount of the technical nano granules used in the 128 ° of 1282345 at o °c: add a surfactant to a reaction solvent, preferably at -3 0 C The addition is carried out at a temperature between -10 ° C, more preferably at a temperature of about -200 ° C, and the reaction solution is stirred for about 20 to 40 minutes, preferably about 30 minutes. In the present invention, the step of forming the micelles is carried out at an extremely low temperature. Therefore, in order to prevent the solvent; the east knot, a solvent mixture including water and an organic solvent is used in the step of forming the micelles. Preferred organic solvents include f alcohol, ethanol, butanol, octanol, nonanol or mixtures thereof; and the water used is preferably distilled water. The ratio of organic solvent to water can be adjusted as appropriate, as long as the solvent does not freeze at the reaction temperature. The organic solvent is preferably used in an amount of from 20% to 40% by weight, based on the total amount of the mixed solvent, and more preferably 3% by weight. When the amount of the organic solvent is less than 2% by weight, the reaction temperature in the step of forming the micelles will not be sufficiently low. When the amount of the organic solvent is more than 4% by weight, the step of forming the micelles cannot be sufficiently performed. In addition, when the temperature at which the micelle is formed is lower than -3 (TC, the micelles will not be formed sufficiently. When the temperature system for forming the micelle is higher, the desired surfactant may not be greatly reduced. The surfactant added to the solvent mixture may be a cationic surfactant, an anionic surfactant, and mixtures thereof. Preferred cationic surfactants include the evolution of octyltrimethylammonium (〇tab), Deuterated trimethylammonium (DeTAB), desertified lauryl tridecyl ammonium (DTAB) and mixtures thereof. Preferred anionic surfactants include sodium dodecyl sulfate (SDS), dioctyl Sodium thiosuccinate and mixtures thereof. The surfactant is preferably used in an amount of from 8 parts to 2.5 parts by weight per part by weight of the solvent mixture. When the amount of surfactant is low At 8 weights,
1282345 化 無法形成微胞。當界面活性劑的用量高於2 · 5份重量時，所 形成的微胞則可能變形成為不欲求的形狀。相較於室溫下微 乳化聚合而言，用於本發明界面活性劑的量係為該室溫下微 乳化聚合所需界面活性劑用量的1 /1 〇。此可能係基於以下事 實：（1)低溫下CMC會下降，因此即使所使用的界面活性劑 量極少，界面活性劑的濃度仍會大於CMC 2 ; (2)包含在該溶 劑混合物中用以防止溶劑凍結的有機溶劑，也可作為共-界面 活性劑（cosurfactant)之用。「CMC」一詞代表「微胞關鍵濃 度（Critical Micelle Concentration)」，其係為藉由界面活性 劑的作用所能形成微胞的該界面活性劑濃度，且所形成微 胞的形狀會隨著該界面活性劑的種類及使用濃度而有所變 。一般來說，當界面活性劑的濃度高過CMc丨之值時， 會形成球體狀微胞；而當界面活性劑的濃度高過cmc 2之 值時，則會形成桿狀或六面體狀的微胞1時，當界面活 性劑的濃度係介於⑽1與CMC2之間時，所得的微胞 在溶液中成透明狀而無法為肉眼告 一 T网田界面活性劑的濃 度係向於CMC 2之值時，所得微 6…、法為肉眼辨識且溶液 成不透明狀。事實上，由肉眼來 雜沾m L 句斷镟胞的形狀是相當困 難的。因此，聚合於微胞中的人 TEM(f ii ^ , K 口物形狀係藉助諸如 透式電子顯微鏡）、SEM(掃描式電 類的儀器進行判斷並據以定出界面 .‘ή鏡）專專之 面活性劑在室@ τ μ ^ j的濃度。當一界1282345 The micelle cannot be formed. When the amount of the surfactant is more than 2.6 parts by weight, the formed micelles may be deformed into an undesired shape. The amount of the surfactant used in the present invention is 1 / 1 of the amount of the surfactant required for the microemulsion polymerization at room temperature as compared with the microemulsion polymerization at room temperature. This may be based on the following facts: (1) CMC will decrease at low temperatures, so even if the surfactant used is very small, the concentration of surfactant will be greater than CMC 2; (2) It is included in the solvent mixture to prevent solvent A frozen organic solvent can also be used as a cosurfactant. The term "CMC" stands for "Critical Micelle Concentration", which is the concentration of the surfactant that can form the micelles by the action of the surfactant, and the shape of the formed cells will follow The type and concentration of the surfactant vary. Generally, when the concentration of the surfactant is higher than the value of CMc, a spherical microcell is formed; and when the concentration of the surfactant is higher than the value of cmc 2, a rod or a hexahedron is formed. In the case of micelle 1, when the concentration of the surfactant is between (10)1 and CMC2, the obtained micelles are transparent in the solution and cannot be visually observed. The concentration of the T-field surfactant is toward CMC. When the value is 2, the obtained micro 6..., the method is visually recognized and the solution is opaque. In fact, it is quite difficult to make the shape of the cell by the naked eye. Therefore, the human TEM (f ii ^ , K mouth shape is transmitted by means of a transmissive electron microscope), SEM (scanning type instrument, and the interface is determined by the scanning electron class). The concentration of the active agent in the chamber @ τ μ ^ j. When a world
隹至，皿下的CMC 1及CMC 2插炎 1及CMC2值即可用於本發明。值為已知時，該CMC 作為傳導性聚 在以界面活性劑形成微胞後，—邊添加可 7 1282345 :正The CMC 1 and CMC 2 inflamed 1 and CMC 2 values under the dish can be used in the present invention. When the value is known, the CMC is used as a conductive polymer. After the micelles are formed by the surfactant, the side can be added as a 7 1282345: positive
I 口物的苯胺單體，一邊攪拌反應溶液。此外，並加入一摻雜 物/、 氧化劑以起始一聚合反應。對每一 1 Q 〇份量之該内含 微胞溶液而言，苯胺單體用量較佳係介於約〇.75份至2·5份 重量間。當苯胺單體用量低於〇·75份重量時，所有的微胞均 無法用作為奈米反應器。當苯胺單體用量高於2·5份重量 時，微胞可能無法接收到全部的苯胺單體，並可能導致微胞 變形。 摻雜物疋用來提尚聚苯胺聚合物的傳導性，並用以調整 反應心液的酸度以加速並穩定反應。摻雜物的範例包括諸如 f氣酸、硫酸、磷酸及其之混合物等等之類的質子型酸。為 提回所製備而成聚合物的傳導性，硫酸較氫氣酸更適合作為 /種摻雜物。對1莫耳的苯胺單體而言，摻雜物的用量較佳 係”於1至3莫耳間。當摻雜物的用量低於丨莫耳時，所製 備而成的聚合物之傳導性可能無法達到令人滿意的程度。當 柘雜物的用置兩於3莫耳時，所製備而成的聚合物之傳導性 並不會隨之等量上升，但卻會導致聚合物變形。 氧化劑係用來聚合苯胺單體，且其範例包括過硫酸銨 ((NHUhhO8)、過氧二硫酸化鉀（loj2)等等。對丨莫耳的苯 胺早體而言，氧化劑的用量較佳係介於0 2至〇 8莫耳間， 更佳係每丨.0莫耳的苯胺單體使用〇·5莫耳的氧化劑。^氧 化劑的用量低於0.2莫耳時，苯胺單體的聚合度可能無法達 到令人滿意的程度。當氧化劑的用量高於〇8莫耳時，苯胺 單體的聚合速度及聚合的效率並不會進一步提高。氧化劑可 被添加到内含苯胺單體及摻雜物的反應溶液中。或者，也可 8 1282345 厂年月曰修(更)正替換頁 --- 以摻雜物（例如氫氣酸、硫酸等等）將氧化劑溶解，並將内含 氧化劑與摻雜物的混合溶液添加到内含苯胺單體的反應溶 液中。更佳疋，該氧化劑與摻雜物係在該内含微胞及苯胺單 體的反應溶液被攪拌約3 0分鐘後才加入。在攪拌過程中， 苯胺單體會被完全併入至微胞内部。聚合反應的時間約為8 至16小時，較佳是約12小時；且反應溫度較佳是維持在與 反應起始溫度相同的溫度下。 在笨的聚合反應完成後，將界面活性劑移除以便分離 出在微胞中生成的聚苯胺奈米顆粒。為移除界面活性劑及反 應副產物，將反應溶液倒入一分離漏斗中，並於其中加入諸 如甲醇、丙酮及其之混合物等等的過量有機溶劑，之後界面 活性劑及反應副產物會溶於該溶劑而進入有機層中。將該上 方有機層丢棄，可得一内含聚苯胺奈米顆粒沉澱的水層。之 後’在室溫下將水蒸發，即可得欲求的聚苯胺奈米顆粒。 從所得聚苯胺奈米顆粒的穿透式電子顯微鏡分析可 知，依據本發明反應條件所形成的奈米顆粒為桿狀且其寬約 2〇奈米長約數百奈米。當溫度下降時，即使使用更高量的界 面活性劑’仍會生成桿狀奈米顆粒。所生成奈米顆粒的傳導 性介於50至200 S/cm間，其係高於室溫下製備而成之奈米 顆粒的傳導性。同時也發現在低溫下，陰離子界面活性劑較 陽離子界面活性劑更適合用來提高聚苯胺奈米顆粒的傳導 性。因此，依據本發明，可以少量界面活性劑至輩出具高傳 導性之桿狀聚苯胺奈米顆粒。 1282345 年月丨曰修(更)正替換頁 7· --———- 下列實施例可進一步說明本發明，但是本發明範疇並不 僅限於此。 [實轭例1 ]以陽_塵土u承氯酸摻雜物在 鼓._反應1度下製備聚笨胺奈米顆粒 以水浴將反應溫度維持在_ 2 〇 °C，並以包含4 〇毫升的蒸 餾水及20毫升的乙醇之溶劑混合物作為反應介質。將〇.5 克作為陽離子界面活性劑的溴化癸基三甲基銨（DeTAB)加到 溶劑混合物中，並攪拌約20分鐘使形成微胞。之後，於反 應溶液中逐滴加入1克的苯胺單體，繼續攪拌反應溶液3〇 分鐘以便將苯胺單體完全併入至微胞内部。同時，將1.125 克的過硫酸銨（氧化劑）溶於6毫升4M的氫氯酸中（苯胺與過 硫酸銨的莫耳比例為1 ··〇· 5)，並將此混合物加到反應溶液 中。在維持反應溫度於-201：之聚合反應起始溫度下的同時， 撥拌反應溶液12小時以將苯胺單體聚合。聚合反應完成後， 將反應溶液倒入一分液漏斗中，於其中加入過量甲醇以溶解 界面活性劑及反應副產物。為獲得聚苯胺奈米顆粒沉澱，以 及I吸掉上方的甲醇層’於室溫下將下方剩餘的水層進行揮 發。以FT-IR確認所形成聚苯胺奈米顆粒。從所得聚苯胺奈 米顆粒的TEM圖可確認所得桿狀聚苯胺奈求顆粒寬約2〇奈 米長約數百奈米。所得聚苯胺奈米顆粒的傳導性界於約5〇 至 80 S/cm 〇 [實施例2] 陽離子界面活性劑及硫酸1雜物在_2(ΓΓ的 瓦度下製備聚茉胺奈来 10 1282345The aniline monomer of the I mouth was stirred while stirring the reaction solution. In addition, a dopant/oxidant is added to initiate a polymerization reaction. The amount of the aniline monomer is preferably from about 〇.75 parts to about 2.5 parts by weight for each of the 1 Q parts of the contained microcell solution. When the amount of aniline monomer is less than 〇·75 parts by weight, all of the micelles cannot be used as a nanoreactor. When the amount of aniline monomer is more than 2.5 parts by weight, the micelles may not receive all of the aniline monomer and may cause deformation of the micelles. The dopant is used to improve the conductivity of the polyaniline polymer and to adjust the acidity of the reaction solution to accelerate and stabilize the reaction. Examples of dopants include protic acids such as f gas, sulfuric acid, phosphoric acid, mixtures thereof and the like. In order to retrieve the conductivity of the prepared polymer, sulfuric acid is more suitable as a dopant than hydrogen acid. For 1 mole of aniline monomer, the amount of dopant is preferably between 1 and 3 moles. When the amount of dopant is lower than that of 丨mol, the prepared polymer is conductive. Sex may not be satisfactory. When the content of the impurities is less than 3 moles, the conductivity of the prepared polymer does not increase with the same amount, but it will cause the polymer to deform. The oxidizing agent is used to polymerize aniline monomers, and examples thereof include ammonium persulfate ((NHUhhO8), potassium peroxydisulfate (loj2), etc. For the aniline precursor of 丨mol, the oxidizing agent is preferably used. The system is between 0 2 and 〇8 mol, more preferably 丨·0 mol of aniline monomer per 丨·5 mol of oxidizing agent. ^ When the amount of oxidizing agent is less than 0.2 mol, the polymerization of aniline monomer The degree may not be satisfactory. When the amount of the oxidizing agent is higher than 〇8 mole, the polymerization rate of the aniline monomer and the polymerization efficiency are not further increased. The oxidizing agent may be added to the aniline monomer and the odorant. The reaction solution of the sundries. Or, can also be 8 1282345 factory year repair (more) is replacing the page - - dissolving the oxidizing agent with a dopant (for example, hydrogen acid, sulfuric acid, etc.), and adding a mixed solution containing the oxidizing agent and the dopant to the reaction solution containing the aniline monomer. More preferably, the oxidizing agent is The dopant is added after the reaction solution containing the micelles and the aniline monomer is stirred for about 30 minutes. During the stirring process, the aniline monomer is completely incorporated into the interior of the micelle. It is 8 to 16 hours, preferably about 12 hours; and the reaction temperature is preferably maintained at the same temperature as the reaction initiation temperature. After the stupid polymerization reaction is completed, the surfactant is removed to separate it in the micro. Polyaniline nanoparticles formed in the cells. To remove the surfactant and reaction by-products, the reaction solution is poured into a separation funnel, and an excess of an organic solvent such as methanol, acetone, a mixture thereof, or the like is added thereto. Thereafter, the surfactant and reaction by-products are dissolved in the solvent and enter the organic layer. The upper organic layer is discarded to obtain an aqueous layer containing precipitated polyaniline nanoparticles. Then 'water at room temperature steam The desired polyaniline nanoparticles can be obtained. From the transmission electron microscopic analysis of the obtained polyaniline nanoparticles, the nanoparticle formed according to the reaction conditions of the present invention is rod-shaped and has a width of about 2 nm. About a few hundred nanometers. When the temperature drops, even if a higher amount of surfactant is used, rod-shaped nanoparticles will be formed. The conductivity of the produced nanoparticles is between 50 and 200 S/cm. The conductivity of nano-particles prepared above room temperature. It is also found that at low temperatures, anionic surfactants are more suitable for improving the conductivity of polyaniline nanoparticles than cationic surfactants. According to the invention, a small amount of surfactant can be used to produce high-conductivity rod-shaped polyaniline nanoparticles. 1282345 丨曰 丨曰 repair (more) replacement page 7 ——————- The following examples can further illustrate the present invention However, the scope of the invention is not limited thereto. [Solid yoke example 1] Preparation of polyamidamine nanoparticles with a cation-dust n-chlorinated dopant at a temperature of 1 degree in a drum. The reaction temperature was maintained at _ 2 〇 ° C in a water bath, and contained 4 〇. A solvent mixture of ML of distilled water and 20 ml of ethanol was used as a reaction medium. 〇.5 g of decyltrimethylammonium bromide (DeTAB) as a cationic surfactant was added to the solvent mixture and stirred for about 20 minutes to form micelles. Thereafter, 1 g of the aniline monomer was added dropwise to the reaction solution, and the reaction solution was further stirred for 3 minutes to completely incorporate the aniline monomer into the inside of the micelle. At the same time, 1.125 g of ammonium persulfate (oxidant) was dissolved in 6 ml of 4 M hydrochloric acid (the molar ratio of aniline to ammonium persulfate was 1 ···· 5), and the mixture was added to the reaction solution. . While maintaining the reaction temperature at the polymerization initiation temperature of -201:, the reaction solution was stirred for 12 hours to polymerize the aniline monomer. After completion of the polymerization, the reaction solution was poured into a separatory funnel, and excess methanol was added thereto to dissolve the surfactant and reaction by-products. In order to obtain precipitation of the polyaniline nanoparticles, and I suck up the upper methanol layer, the remaining aqueous layer below is volatilized at room temperature. The formed polyaniline nanoparticles were confirmed by FT-IR. From the TEM image of the obtained polyaniline nanoparticles, it was confirmed that the obtained rod-shaped polyaniline had a particle width of about 2 Å and a length of about several hundred nanometers. The conductivity of the obtained polyaniline nanoparticles is about 5 〇 to 80 S/cm 〇 [Example 2] The cationic surfactant and the sulfuric acid 1 impurity are prepared at _2 (the valence of yttrium). 1282345
、 ，巫蚁钓界面活性劑外， 並以10毫升2 Μ的硫酸作為摻雜物外，芙太μ W r丞本上依照實施例1 所述方法進行製備。同樣以FT_IR確認所形成聚苯胺奈米顆 粒。從所得聚苯胺奈米顆粒的丁EM圖可確認所得聚苯胺奈 米顆粒形狀為桿狀，且寬約數十奈米長約數百奈米。 [實施例3] 物在_2(rc的 度下製備聚装胺奈来顆1 除了以〇·3克的十二烷基硫酸鈉（陰離子界面活性劑）作 為界面活性劑，並以10毫升2M的硫酸作為摻雜物外，基本 上依照實施例i所述方法進行製備。同樣以？1以確認所形 成聚苯胺奈米顆粒。從所得聚苯胺奈米顆粒的TEM圖可確 認所得聚苯胺奈米顆粒為桿狀，且寬約數十奈米長约數百奈 米。所得聚苯胺奈米顆粒的傳導性介於約15〇至2〇〇 s/cm， 其係較以陽離子界面活性劑所製備而成的聚苯胺奈米顆粒 的傳導性來得高。 如上述’依據本發明製備聚苯胺奈米顆粒的方法，其之 微乳化聚合係於極低的溫度下（约_2(rc)執行。因此，相較於 至溫下微乳化聚合而言，用於本發明界面活性劑的量係為該 至Λ下微乳化聚合所需界面活性劑用量的丨/丨0，因此可大幅 降低製備聚苯胺奈米顆粒所需的成本，並提高其產率。由於 本發明所需使用的界面活性劑量較低，因此也可大幅簡化清 洗微胞以將界面活性劑與所得聚苯胺奈米顆粒分離的製 1282345 f__^ f. B ,'J修次)正替換Ϊ 程。詳言之，清洗步驟中的溶劑用量及 此外，依據本發明方法製備而成的聚苯 於200至300 S/cm間之高傳導性，且 劑、電磁屏障、磁記錄媒體、氣體感應 子傳輸層等等之類的電磁材料是非常有 形’因此特別可用作為一種微電乡覽、一 等等。 本發明參照實施例已詳述如上，但 解除所揭示實施例外’本發明尚可作許 換，該等變化及替換仍屬附隨之申請專 【圖式簡單說明】 【元件代表符號簡單說明】 -處理時間也將縮減。 .胺奈米顆粒之具有介 其可作為諸如抗-靜電 ，器、發光裝置中的電 •用的。且由於其為桿 種碳纖材料的替代物 習知技藝人士應能了 多等效變化及等效替 利範圍的範疇。 12The witches were squirted with the surfactant and prepared by using the method described in Example 1 except that 10 ml of 2 硫酸 sulfuric acid was used as the dopant. The formed polyaniline nanoparticles were also confirmed by FT_IR. From the EM image of the obtained polyaniline nanoparticles, it was confirmed that the obtained polyaniline nanoparticles had a rod shape and a width of about several tens of nanometers and a length of several hundreds of nanometers. [Example 3] Preparation of polyaluminate 1 at rc (except for rc 3 g of sodium lauryl sulfate (anionic surfactant) as a surfactant, and 10 ml 2M sulfuric acid was used as a dopant, and it was prepared substantially in accordance with the method described in Example i. The formed polyaniline nanoparticles were also confirmed by ?1. The obtained polyaniline was confirmed from the TEM image of the obtained polyaniline nanoparticles. The nano particles are rod-shaped and have a width of about several tens of nanometers and a length of about several hundred nanometers. The obtained polyaniline nanoparticles have a conductivity of about 15 〇 to 2 〇〇 s/cm, which is a cationic surfactant. The prepared polyaniline nanoparticles have high conductivity. As described above, the method for preparing polyaniline nanoparticles according to the present invention is microemulsified polymerization at a very low temperature (about _2 (rc) Therefore, compared with the sub-temperature microemulsion polymerization, the amount of the surfactant used in the present invention is 丨/丨0 of the amount of the surfactant required for the submerged microemulsification polymerization, and thus can be greatly reduced. The cost of preparing polyaniline nanoparticles and increasing their yield. The amount of interfacial activity required for the present invention is low, so that the cleaning of the micelles to separate the surfactant from the obtained polyaniline nanoparticles can be greatly simplified, and the 1282345 f__^ f. B, 'J repair times) are replaced. In particular, the amount of solvent used in the cleaning step and, in addition, the high conductivity of polystyrene prepared according to the method of the present invention between 200 and 300 S/cm, and the agent, electromagnetic barrier, magnetic recording medium, gas The electromagnetic material such as the inductive sub-transport layer or the like is very tangible' and thus is particularly useful as a micro-electricity, one, etc. The present invention has been described in detail above with reference to the embodiments, but the disclosed embodiments are omitted. For the change, the changes and replacements are still attached to the application. [Simple description of the diagram] [Simple description of the symbol of the component] - The processing time will also be reduced. The amine nanoparticles can be used as anti- Electrostatics, devices, and illuminators are used in electrical applications, and because they are alternatives to carbon fiber materials, those skilled in the art should be able to vary the range of equivalents and equivalents.