TWI439415B - A method for producing composite material containing carbon nanotubes and polyester and its products - Google Patents
A method for producing composite material containing carbon nanotubes and polyester and its products Download PDFInfo
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本發明係關於一種奈米材料備製技術，尤其是一種以酯交換法備製出結合有奈米碳管的聚酯複合材料的製造方法及其製品。The invention relates to a nano material preparation technology, in particular to a method for preparing a polyester composite material combined with a carbon nanotube by a transesterification method and a product thereof.
奈米碳管是日本飯島澄男教授在1991年以穿透式電子顯微鏡觀察碳的團簇時意外發現的。奈米碳管是由碳原子中sp2 軌域鍵結而成五邊形及六邊形之網狀結構，其兩端可視為一個碳六十剖半所構成之封閉端，其是一層或多層的未飽和石墨層(graphite layer)捲繞而成之中空管狀物，而奈米碳管一般依組成結構分為單壁碳管(single-wall carbon nanotube,SWNT)和多壁碳管(multil-wall carbon nanotube,MWNT)。單壁奈米碳管之直徑大約在0.4至2奈米(nm)，多壁奈米碳管之直徑大約在10至50nm，長度可達數微米(μm)至數十微米之間，而具有較好的長徑比。奈米碳管基於其碳原子在奈米碳管中的排列結構不同，可使其具有獨有的特性，因而具有相當大的應用潛力，其獨有的特性包括：擁有較大的長徑比、獨特的導電、導熱、機械與電性質，以致可應用於氫氣儲存、電極材料、場發射平面顯示器、化學偵測器、奈米級溫度計、微探針與其他複合材料等。此外，藉由奈米碳管良好的導電性、導熱性與機械強度，並可做為強化高分子材料之添加劑。The carbon nanotubes were accidentally discovered by Professor Iijima, a Japanese professor of carbon clusters observed in 1991 by a transmission electron microscope. Is the junction carbon nanotube sp 2 orbitals of atoms bonded to each of the pentagonal and hexagonal mesh structure, both ends thereof may be regarded as a sixty-sectional half closed end formed of carbon, which is one or more A multi-layered unsaturated graphite layer is formed by winding a hollow tube, and the carbon nanotubes are generally classified into a single-wall carbon nanotube (SWNT) and a multi-wall carbon tube (multil) according to the composition. -wall carbon nanotube, MWNT). The single-walled carbon nanotubes have a diameter of about 0.4 to 2 nanometers (nm), and the multi-walled carbon nanotubes have a diameter of about 10 to 50 nm and a length of several micrometers (μm) to several tens of micrometers. Better aspect ratio. The carbon nanotubes have different characteristics due to their different arrangement of carbon atoms in the carbon nanotubes, so they have considerable application potential. Their unique characteristics include: having a large aspect ratio. Unique conductivity, thermal conductivity, mechanical and electrical properties, so that it can be applied to hydrogen storage, electrode materials, field emission flat panel displays, chemical detectors, nanometer thermometers, microprobes and other composite materials. In addition, the carbon nanotubes have good electrical conductivity, thermal conductivity and mechanical strength, and can be used as an additive for reinforcing polymer materials.
由上述可見，現有技術的奈米碳管具有前述各方面的廣大應用潛力，然而已知其仍具有下述限制及缺點：奈米碳管在與高分子材料混合製作過程中，碳管與高分子間的作用力低，且碳管本身不溶於水與溶劑中，又碳管之間存在具有較強的凡得瓦力(Van der Waals force)作用，而易產生糾結聚集的情況，因而有分散性不足的問題。以目前關於奈米碳管的複合材之相關技術而言，大部分之技術都僅對奈米碳管做酸化處理，而導致奈米碳管無法均勻分散於高分子基材中。據以，現有技術仍缺乏一種具有高度分散性之含奈米碳管的高分子複合材料。It can be seen from the above that the prior art carbon nanotubes have the broad application potential of the foregoing various aspects, but it is known to have the following limitations and disadvantages: the carbon nanotubes are high in the process of mixing the carbon nanotubes with the polymer material. The interaction between the molecules is low, and the carbon tube itself is insoluble in water and solvent, and there is a strong Van der Waals force between the carbon tubes, which is easy to produce entanglement and aggregation. The problem of insufficient dispersion. In the current technology related to the composite of carbon nanotubes, most of the techniques only acidify the carbon nanotubes, and the carbon nanotubes cannot be uniformly dispersed in the polymer substrate. Accordingly, the prior art still lacks a highly dispersible polymer composite material containing carbon nanotubes.
為解決目前奈米碳管於製作過程中僅將奈米碳管進行酸化處理，而會產生分散性問題，導致碳管無法均勻分散於高分子基材中，進而無法有效量產奈米碳管，本發明係提供一種含奈米碳管與聚酯之複合材料的製造方法，其係藉由酯交換法，將奈米碳管嫁接到聚酯類高分子材料上，以獲得物性、導電性及穩定性良好之複合材料。In order to solve the problem that only the carbon nanotubes are acidified in the production process of the nano carbon tubes, dispersibility problems may occur, and the carbon tubes cannot be uniformly dispersed in the polymer substrate, so that the carbon nanotubes cannot be efficiently produced. The present invention provides a method for producing a composite material comprising a carbon nanotube and a polyester, which is obtained by grafting a carbon nanotube onto a polyester polymer material by a transesterification method to obtain physical properties and conductivity. And a composite with good stability.
本發明所提供的技術手段在於提供一種含奈米碳管與聚酯之複合材料的製造方法，其係包括有下列步驟：取一奈米碳管與酸性溶液混合反應得一酸化奈米碳管；將該酸化奈米碳管分散於一有機溶劑中，再加入一含有長烷基鏈段的改質劑及一脫水劑，完全反應後得一改質奈米碳管；將該改質奈米碳管分散於一聚酯有機混合溶液中，再加入一酯交換劑混合反應，藉以將該改質奈米碳管嫁接到該聚酯有機混合溶液中的聚酯分子鏈上，得到一改質含奈米碳管與聚酯之複合材料。The technical means provided by the present invention is to provide a method for manufacturing a composite material comprising a carbon nanotube and a polyester, comprising the steps of: taking a carbon nanotube and mixing with an acidic solution to obtain an acidified carbon nanotube; Dissolving the acidified carbon nanotube in an organic solvent, adding a modifier containing a long alkyl segment and a dehydrating agent, and completely reacting to obtain a modified carbon nanotube; The carbon nanotubes are dispersed in a polyester organic mixed solution, and then an ester exchanger is mixed to react, thereby grafting the modified carbon nanotubes onto the polyester molecular chain in the polyester organic mixed solution, thereby obtaining a modification. A composite of carbon nanotubes and polyester.
較佳的，所述之有機溶劑係高沸點的極性(親水性)非質子性溶劑。Preferably, the organic solvent is a high boiling polar (hydrophilic) aprotic solvent.
較佳的，所述之含奈米碳管與聚酯之複合材料的製造方法，其中該含有長烷基鏈段的改質劑係包含有碳數12以上長碳鏈烷醇或聚醚胺，諸如，但不限於Jeffamine，更佳的，該含有長烷基鏈段的改質劑是十八烷醇或聚醚胺。Preferably, the method for producing a composite material comprising a carbon nanotube and a polyester, wherein the modifier containing a long alkyl segment comprises a long carbon alkanol or a polyether amine having a carbon number of 12 or more Such as, but not limited to, Jeffamine More preferably, the modifier containing a long alkyl segment is stearyl alcohol or a polyether amine.
較佳的，所述之含奈米碳管與聚酯之複合材料的製造方法，其中該脫水劑係包含有N,N’-二環己基碳二亞胺(N,N’-dicyclohexyl-carbodiimide,DCC)、醋酸酐、磷酸酐、多磷酸、磷酸、焦硫酸、硫酸、氯磺酸、氧化鋅或無水硫酸銅，但不限於：N,N’-二環己基碳二亞胺(N,N’-dicyclohexyl-carbodiimide,DCC)。Preferably, the method for producing a composite material comprising a carbon nanotube and a polyester, wherein the dehydrating agent comprises N, N'-dicyclohexylcarbodiimide (N, N'-dicyclohexyl-carbodiimide , DCC), acetic anhydride, phosphoric anhydride, polyphosphoric acid, phosphoric acid, pyrosulfuric acid, sulfuric acid, chlorosulfonic acid, zinc oxide or anhydrous copper sulfate, but not limited to: N, N'-dicyclohexylcarbodiimide (N, N'-dicyclohexyl-carbodiimide, DCC).
較佳的，所述之含奈米碳管與聚酯之複合材料的製造方法，其中該聚酯有機混合溶液可為，但不限於：配於氯仿中的聚酯溶液。Preferably, the method for producing a composite material comprising a carbon nanotube and a polyester, wherein the polyester organic mixed solution is, but not limited to, a polyester solution formulated in chloroform.
較佳的，所述之含奈米碳管與聚酯之複合材料的製造方法，其中該酯交換劑係包含有四丁基鈦酸酯[Ti(OBu)4 ]、四異丙基鈦酸酯、鎂、氧化鈣、鹼性氧化鋁、有機酸、醋酸鈷、醋酸鎂、醋酸鈣或醋酸錳，但不限於：四丁基鈦酸酯[Ti(OBu)4 ]。Preferably, the method for producing a composite material comprising a carbon nanotube and a polyester, wherein the ester exchanger comprises tetrabutyl titanate [Ti(OBu) 4 ], tetraisopropyl titanic acid Ester, magnesium, calcium oxide, basic alumina, organic acid, cobalt acetate, magnesium acetate, calcium acetate or manganese acetate, but not limited to: tetrabutyl titanate [Ti(OBu) 4 ].
較佳的，所述之含奈米碳管與聚酯之複合材料的製造方法，其中該改質奈米碳管之含量係介於該改質含奈米碳管與聚酯之複合材料之整體重量的0.5%至4.0%之間。Preferably, the method for manufacturing a composite material comprising a carbon nanotube and a polyester, wherein the content of the modified carbon nanotube is between the modified composite material comprising a carbon nanotube and a polyester The overall weight is between 0.5% and 4.0%.
較佳的，所述之含奈米碳管與聚酯之複合材料的製造方法，其中該改質奈米碳管之含量係約為該改質含奈米碳管與聚酯之複合材料之整體重量的3.0%。Preferably, the method for manufacturing a composite material comprising a carbon nanotube and a polyester, wherein the content of the modified carbon nanotube is about the composite material of the modified carbon nanotube-containing polyester and the polyester 3.0% of the overall weight.
本發明所提供的技術手段在於提供一種改質含奈米碳管與聚酯之複合材料，其係由一種如前所述之含奈米碳管與聚酯之複合材料的製造方法所製成。The technical means provided by the present invention is to provide a modified composite material comprising a carbon nanotube and a polyester, which is made by a manufacturing method of a composite material comprising a carbon nanotube and a polyester as described above. .
較佳的，所述之改質含奈米碳管與聚酯之複合材料，其中該改質奈米碳管之含量係佔該改質含奈米碳管與聚酯之複合材料整體重量約3.0%，其表面電阻降低至10-1 Ω/cm2 以下，在200 MHZ頻率之電場下的電磁波遮蔽效率達到20%至65%之間。Preferably, the modified carbon nanotube-polyester composite material comprises the modified nanocarbon tube in an amount corresponding to the overall weight of the modified carbon nanotube-containing composite material. 3.0%, the surface resistance is reduced to 10 -1 Ω/cm 2 or less, and the electromagnetic wave shielding efficiency at an electric field of 200 MHZ is between 20% and 65%.
本發明所提供之含奈米碳管與聚酯之複合材料的製造方法及其製品，可以獲得的優點和功效增進有：The method for producing a composite material comprising a carbon nanotube and a polyester provided by the invention and the product thereof can be improved in advantages and effects:
1、該奈米碳管經過酸化後再添加入改質劑，藉由該奈米碳管表面官能基化(functionalization)之改質方式來幫助奈米碳管在溶劑中或水中均勻分散，並提升與高分子基材中的相容性，且能以少量的添加奈米碳管就可提升複合材本身所缺乏的優越性能。1. The carbon nanotube is acidified and then added to the modifier to modify the surface functionalization of the carbon nanotube to help the carbon nanotubes to be uniformly dispersed in the solvent or in water, and Improve the compatibility with the polymer substrate, and the addition of a small amount of carbon nanotubes can improve the superior performance of the composite itself.
2、本發明以具有長烷基鏈段的十八烷醇或聚醚胺作為改質劑，並同時添加少量的酯交換劑，使碳管與聚酯之間形成化學鍵結以有效增強材料之機械以及物理性質，接著藉由熔融過程來製備聚酯與多壁奈米碳管複合材料，由於其具有加工容易、操作簡單且可大量生產以及成本較低等優點，相當適合應用於塑膠工業。2. The invention uses octadecyl alcohol or polyether amine having a long alkyl segment as a modifier, and simultaneously adds a small amount of a transesterification agent to form a chemical bond between the carbon tube and the polyester to effectively enhance the material. Mechanical and physical properties, followed by the melt process to prepare polyester and multi-walled carbon nanotube composites, because of its advantages of easy processing, simple operation, mass production and low cost, it is quite suitable for the plastics industry.
本發明將由下列的實驗備製流程及實施例作進一步的說明，熟知本發明之技藝者，可以做些許的改良與修飾，但不脫離本發明的範疇。The invention will be further clarified by the following experimental preparations and examples, and those skilled in the art can make some modifications and modifications without departing from the scope of the invention.
本發明以多壁碳管為製備對象，所述及的碳管均指多壁碳管，下述實驗備製流程中所述及各樣品成分比例及代號請參閱表1：The invention adopts a multi-wall carbon tube as a preparation object, and the carbon tubes mentioned above all refer to multi-wall carbon tubes, and the proportions and codes of the sample components described in the following experimental preparation process are shown in Table 1:
【實施例一】[Embodiment 1]
1、改質奈米碳管之備製1. Preparation of modified carbon nanotubes
取一多壁原始奈米碳管(u-CNT)，該多壁原始奈米碳管係由台灣辛耘企業股份有限公司所提供，取該多壁原始奈米碳管約2.5 g置於500 ml的圓底燒瓶中，加入約375 ml,12 N的硝酸溶液(HNO3(aq) )中，利用磁石攪拌使碳管分散均勻，於120℃下迴流40分鐘，並在室溫(約25℃)下攪拌2小時後，將其倒入蒸餾水中稀釋，靜置48小時，待其沈澱，將上層的澄清酸液移除；下層含碳管酸液則添加蒸餾水反覆進行清洗、靜置沈澱、上層澄清酸液移除的步驟，直到pH值達到中性(pH約6至7)，利用玻璃過濾裝置進行抽氣過濾，在50℃下以真空烘箱移除多餘水份之後藉由粉碎機將濾餅粉碎後可得到一酸化奈米碳管(CNT-COOH)；再取約1 g的酸化奈米碳管(CNT-COOH)分散在約150 ml的無水二甲基甲醯胺(dimethyl formamide,DMF)有機溶液中攪拌1小時，加入過量的十八烷醇(stearyl alcohol)約3 g以上，以超音波震盪、攪拌，待十八烷醇完全溶解，再加入過量的脫水劑N,N’-二環己基碳二亞胺(N,N’-dicyclohexyl-carbodiimide,DCC)約3 g以上，在室溫下反應，超音波震盪3小時，再持續攪拌45小時後，利用玻璃過濾裝置進行抽氣過濾，利用大量DMF將過量的十八烷醇及DCC徹底清洗乾淨，即可獲得一改質奈米碳管(CNT-18)。Taking a multi-walled raw carbon nanotube (u-CNT), the multi-walled raw carbon nanotube system is provided by Taiwan Xinyi Enterprise Co., Ltd., and the multi-walled raw carbon nanotube is placed at 500 g. In a round bottom flask of ml, add about 375 ml of 12 N nitric acid solution (HNO 3 (aq) ), stir the carbon tube by magnet stirring, reflux at 120 ° C for 40 minutes, and at room temperature (about 25 After stirring for 2 hours at ° C), it was poured into distilled water and diluted, and allowed to stand for 48 hours. After it was precipitated, the upper layer of the clarified acid solution was removed; the lower layer of the carbon-containing tube acid solution was repeatedly washed with distilled water and allowed to stand for precipitation. The upper layer clarifies the acid removal step until the pH reaches neutral (pH about 6 to 7), and uses a glass filter device for suction filtration, and removes excess water in a vacuum oven at 50 ° C. After crushing the filter cake, an acidified carbon nanotube (CNT-COOH) can be obtained; and about 1 g of acidified carbon nanotube (CNT-COOH) is dispersed in about 150 ml of anhydrous dimethylformamide (dimethyl). Formamide, DMF) stir in organic solution for 1 hour, add excess stearyl alcohol about 3 g or more, with ultrasonic vibration Stir, until the octadecyl alcohol is completely dissolved, and then add an excess of the dehydrating agent N, N'-dicyclohexyl-carbodiimide (DCC) about 3 g or more, and react at room temperature. Ultrasonic vibration for 3 hours, and then stirring for 45 hours, using a glass filter device for suction filtration, using a large amount of DMF to thoroughly clean excess stearyl alcohol and DCC to obtain a modified carbon nanotube ( CNT-18).
2、聚酯/奈米碳管複合材料之製備2. Preparation of polyester/nano carbon tube composite
請參閱附件1所示，首先取約50 g的聚酯(B)與約500 ml的氯仿(Chloroform)混合，經由超音波震盪和磁石攪拌使聚酯完全溶解於氯仿中，分別秤取原始奈米碳管(u-CNT)(A)及改質奈米碳管(CNT-18)(A')佔整體複合材料重量百分率約0.5 wt%、1.5 wt%、3 wt%，並各別分散在適量氯仿中，超音波震盪1小時使其分散均勻，加入預先溶解於氯仿之聚酯中，持續超音波震盪2小時，再攪拌2小時，待其分散均勻後，不同濃度(0.5 wt%、1.5 wt%、3 wt%)的原始奈米碳管(u-CNT)(A)及改質奈米碳管(CNT-18)(A')分別與聚酯反應後所得的樣品，將各樣品倒於鐵盤內並置於抽氣櫃中一晚使氯仿抽乾，再放入烘箱中以70℃烘乾4小時，取出各樣品，將各樣品剪碎後，以180℃、50每分轉數(r.p.m)的條件進行熔融混煉5分鐘，即可得到聚酯/奈米碳管複合材料(C)，即PC系列及PC-18系列，請參見表1所述之PC系列(聚酯/原始奈米碳管複合材料)及PC-18系列(聚酯/改質奈米碳管複合材料)。Please refer to the attached item 1. Firstly, about 50 g of polyester (B) is mixed with about 500 ml of chloroform (Chloroform), and the polyester is completely dissolved in chloroform by ultrasonic vibration and magnet stirring. The carbon nanotubes (u-CNT) (A) and the modified carbon nanotubes (CNT-18) (A') account for about 0.5 wt%, 1.5 wt%, and 3 wt% of the total composite weight, and are dispersed separately. In an appropriate amount of chloroform, the ultrasonic wave was shaken for 1 hour to make it evenly dispersed. The polyester was pre-dissolved in chloroform, and the ultrasonic vibration was continued for 2 hours, and then stirred for 2 hours. After being uniformly dispersed, different concentrations (0.5 wt%, 1.5 wt%, 3 wt%) of the original carbon nanotubes (u-CNT) (A) and modified carbon nanotubes (CNT-18) (A') respectively, after reacting with the polyester, each sample will be The sample was poured into an iron pan and placed in a suction cabinet for one night to drain the chloroform, then placed in an oven and dried at 70 ° C for 4 hours. Each sample was taken out, and each sample was cut into pieces at 180 ° C, 50 minutes per minute. The number of revolutions (rpm) is melt-kneaded for 5 minutes to obtain a polyester/nanocarbon tube composite (C), that is, a PC series and a PC-18 series. Please refer to the PC series described in Table 1. Ester/original nano Carbon tube composite) and PC-18 series (polyester / modified carbon nanotube composite).
3、聚酯/改質多壁奈米碳管/酯交換劑複合材料之製備3. Preparation of polyester/modified multi-walled carbon nanotube/ester exchanger composite
請參閱圖1及附件2所示，首先取約50 g的B(聚酯)與約500 ml的氯仿(Chloroform)混合，經由超音波震盪和磁石攪拌使聚酯完全溶解於氯仿中，分別取改質奈米碳管(CNT-18)(A')佔整體複合材料重量百分率約0.5 wt%、1.5 wt%、3 wt%，並各別分散在適量氯仿中，以超音波震盪1小時使其分散均勻，加入預先溶解於氯仿之聚酯中，經超音波震盪、攪拌各1小時後，添加酯交換劑四丁基鈦酸酯[Ti(OBu)4 ]，持續超音波震盪2小時、攪拌2小時，待其分散均勻後，不同濃度(0.5 wt%、1.5 wt%、3 wt%)的改質奈米碳管(CNT-18)(A')分別與聚酯及酯交換劑反應後所得的樣品，將該樣品倒於鐵盤內並置於抽氣櫃中一晚使氯仿抽乾，再放入烘箱中以70℃烘乾4小時，取出該樣品並剪碎，以180℃、50 r.p.m的條件進行熔融混煉5分鐘，即可得到含奈米碳管與聚酯之複合材料(D)，即表1所述之PC-18T系列(聚酯/改質奈米碳管/酯交換劑複合材料)。Referring to Figure 1 and Figure 2, firstly, about 50 g of B (polyester) is mixed with about 500 ml of chloroform (Chloroform), and the polyester is completely dissolved in chloroform by ultrasonic vibration and magnet stirring. The modified carbon nanotubes (CNT-18) (A') accounted for about 0.5 wt%, 1.5 wt%, and 3 wt% of the total composite weight, and were dispersed in an appropriate amount of chloroform, so that the ultrasonic wave was shaken for 1 hour. The dispersion was uniform, and the polyester which was previously dissolved in chloroform was added, and after ultrasonic vibration and stirring for 1 hour, the transesterification agent tetrabutyl titanate [Ti(OBu) 4 ] was added, and the ultrasonic vibration was continued for 2 hours. After stirring for 2 hours, after being uniformly dispersed, different concentrations (0.5 wt%, 1.5 wt%, 3 wt%) of modified carbon nanotubes (CNT-18) (A') were respectively reacted with polyester and transesterification agent. After the obtained sample, the sample was poured into an iron pan and placed in a suction cabinet for one night to dry the chloroform, and then dried in an oven at 70 ° C for 4 hours, the sample was taken out and cut, at 180 ° C, Melt kneading at 50 rpm for 5 minutes to obtain a composite material (D) containing carbon nanotubes and polyester, namely PC-18T series (polyester/modified nano) described in Table 1. Tube / transesterification agent composites).
4、奈米碳管分散性分析4, carbon nanotube dispersion analysis
分別稱取改質前、後的多壁奈米碳管(u-CNT及CNT-18)約2 mg，各別分散於20 ml水和有機溶劑中，經超音波震盪30小時後觀察其分散結果。結果呈現原始奈米碳管(u-CNT)不論分散在水或氯仿中最後都會沉澱，而經過酸化處理後的酸化奈米碳管(CNT-COOH)由於碳管表面接枝羧基而使其具有親水性，導致可以分散在水中，但較不易分散在氯仿中且會形成沉澱，而改質奈米碳管(CNT-18)因其具有長碳氫鏈段，屬於疏水性可以均勻分散在氯仿中，而藉由碳管在有機溶劑中的分散性可以證明十八烷醇已成功的接枝到碳管上。Weigh about 2 mg of multi-walled carbon nanotubes (u-CNT and CNT-18) before and after the modification, respectively, dispersed in 20 ml of water and organic solvent, and observed for dispersion after ultrasonic oscillation for 30 hours. result. As a result, the original carbon nanotubes (u-CNTs) are precipitated in water or chloroform, and the acidified carbon nanotubes (CNT-COOH) after acidification have a carboxyl group on the surface of the carbon nanotubes. Hydrophilic, which can be dispersed in water, but less dispersed in chloroform and precipitates. The modified carbon nanotube (CNT-18) is hydrophobic and can be uniformly dispersed in chloroform because of its long hydrocarbon segment. However, the octadecyl alcohol has been successfully grafted onto the carbon tube by the dispersibility of the carbon tube in an organic solvent.
藉由動態機械分析(Dynamic Mechanical Analysis,DMA)分析研究本發明複合材料的儲存模數(Storage Modulus,E')、損失模數(Loss Modulus,E")，前述之等模數係可為一般DMA儀器即可分析顯示之數據，本發明所使用的DMA儀器(TA Instruments Q800)，其中儲存模數E'主要是探討複合材料的剛性和強度(抗折強度)，損失模數E"則主要是探討材料的黏彈性質(將振動能轉換為熱能)、柔韌性以及玻璃轉移溫度(Tg )。原始奈米碳管、改質奈米碳管、添加酯交換劑的改質奈米碳管，此三種奈米複合材料的DMA分析圖，將其數據整理於表2，可以得知隨著碳管的含量增加，三個系列複合材之儲存模數(E')相對都提升，表示添加奈米碳管後，由於奈米碳管屬於一種長管結構，其會與長纖化高分子性質類似，應力可以藉由兩相之間互相傳遞，因而提升複合材料之剛性。由表2可以發現奈米碳管經十八烷醇改質後，其E'隨著碳管含量增加而提升，且比原始奈米碳管之奈米複合材表現佳。The storage modulus (E') and the loss modulus (Loss Modulus, E") of the composite material of the present invention are analyzed by Dynamic Mechanical Analysis (DMA), and the above-mentioned modulus system can be general. The DMA instrument can analyze the displayed data. The DMA instrument (TA Instruments Q800) used in the present invention, in which the storage modulus E' is mainly to investigate the rigidity and strength (deformation strength) of the composite material, the loss modulus E" is mainly It is to explore the viscoelastic properties of materials (convert vibration energy into heat), flexibility and glass transition temperature (T g ). Raw carbon nanotubes, modified carbon nanotubes, modified carbon nanotubes with ester exchangers, DMA analysis of the three nanocomposites, and their data are summarized in Table 2, The content of the tube is increased, and the storage modulus (E') of the three series of composite materials is relatively increased, indicating that after the addition of the carbon nanotubes, since the carbon nanotubes belong to a long tube structure, they will be related to the properties of the long-fibrillated polymer. Similarly, stress can be transferred between the two phases, thereby increasing the rigidity of the composite. It can be seen from Table 2 that after modification of the carbon nanotubes with stearyl alcohol, the E' increases as the carbon tube content increases, and performs better than the nanocomposite of the original carbon nanotubes.
而添加3 wt%的CNT-18之複合材料在40℃下，其剛性可提升77.4%，提升之原因主要是因為藉由十八烷醇改質後，碳管在聚酯中可達到較均勻之分散，且增進碳管與聚酯之間的相互作用力。另外，發現添加3%的PC-18T之酯交換劑複合材料，其剛性可提升88%左右。顯示在反應過程中加入酯交換劑，可使E'提升幅度更大，表示添加酯交換劑能夠更進一步增進改質碳管與聚酯之間的相互作用力。The addition of 3 wt% CNT-18 composites can increase the rigidity by 77.4% at 40 °C. The reason for the increase is mainly because the carbon nanotubes can be more uniform in the polyester after upgrading with stearyl alcohol. Disperse and enhance the interaction between the carbon tube and the polyester. In addition, it was found that the addition of 3% PC-18T ester exchanger composite increased the rigidity by about 88%. It is shown that the addition of the transesterification agent during the reaction can increase the E' increase, indicating that the addition of the transesterification agent can further enhance the interaction between the modified carbon tube and the polyester.
而添加0.5 wt%以及1.5 wt%之原始奈米碳管，其E'數值只提升23.3%及43.3%，且當原始奈米碳管添加至3wt%時，其只能提升約58.8%左右，與改質奈米碳管比較，提升幅度已明顯有較緩慢的情況產生。Adding 0.5 wt% and 1.5 wt% of the original carbon nanotubes, the E' value only increased by 23.3% and 43.3%, and when the original carbon nanotubes were added to 3 wt%, it only increased by about 58.8%. Compared with the modified carbon nanotubes, the increase has obviously been slower.
原始奈米碳管、改質奈米碳管、添加酯交換劑的改質奈米碳管，此三種奈米複合材料的損失模數(E")與溫度關係圖，將複合材料損失模數(E")數據整理於表3。可得知，當奈米碳管含量越多時，其損失模數(E")相對也會提升，是由於奈米碳管本身是由同心管套裝而成之結構，內部為中空，其可藉由體積變化來呈現其彈性，可承受大於40%拉伸應變之性質，並藉由其中空部份的塌陷具有吸收較大能量的特性，並提升複合材料之韌性(toughness)。而添加3 wt%的改質奈米碳管，其損失模數(E")提升43.8%，比原始奈米碳管複合材料之33.6%還要來的高。且添加3%的PC-18T之酯交換劑複合材料，其損失模數(E")更能大幅提升75.6%左右，表示添加酯交換劑能夠有效提升改質奈米碳管與聚酯之間的交互作用並增加奈米複合材的柔韌性。Raw carbon nanotubes, modified carbon nanotubes, modified carbon nanotubes with ester exchangers, loss modulus (E") and temperature relationship of the three nanocomposites, loss modulus of composites The (E") data is organized in Table 3. It can be known that when the content of the carbon nanotubes is larger, the loss modulus (E") is also relatively increased, because the carbon nanotube itself is a structure made up of concentric tubes, and the interior is hollow, which can be It exhibits its elasticity by volume change, can withstand the properties of tensile strain greater than 40%, and has the property of absorbing large energy by the collapse of the hollow portion, and enhances the toughness of the composite. The wt% modified carbon nanotubes have a 43.8% increase in loss modulus (E"), which is higher than the 33.6% of the original carbon nanotube composite. And adding 3% PC-18T ester exchanger composite, the loss modulus (E") can be greatly increased by about 75.6%, indicating that the addition of transesterification agent can effectively improve the between modified carbon nanotubes and polyester. The interaction and increase the flexibility of the nanocomposite.
5、聚酯/奈米碳管複合材料導電性質分析5. Analysis of conductive properties of polyester/nano carbon nanotube composites
以石化製備而成之塑膠，由於其具有質量輕、易加工以及價格便宜等優點，而被廣泛應用於民生工業，但由於其本身屬於絕緣物質，所以容易在加工過程形成摩擦而產生靜電，對於工業上尤其在電子包裝業與科技業方面是不可行的。而奈米碳管是經由碳原子sp2 混成為主，具有π電子網路，碳管管壁的彎曲，使的電荷傳遞會比石墨來的快，而導電性介於導體與半導體之間，其具有獨特之導電性質。為了要降低靜電對於複合材料的危害，將奈米碳管導入聚酯形成奈米複合材料後，其會在系統內形成導電網路，而降低高分子基材的電阻值，是由於碳奈米管間的彼此接觸使得電子會從碳奈米管表面之共軛電子快速傳遞，並可將多餘的電荷釋放出來，而使複合材料具有抗靜電效果。The plastic prepared by petrochemical is widely used in the people's livelihood industry because of its advantages of light weight, easy processing and low price. However, since it is an insulating material, it is easy to form friction during processing to generate static electricity. Industrially, it is not feasible in the electronic packaging industry and the technology industry. The carbon nanotubes are mixed by the carbon atom sp 2 and have a π electron network. The carbon tube wall is bent, so that the charge transfer is faster than that of the graphite, and the conductivity is between the conductor and the semiconductor. It has unique conductive properties. In order to reduce the harm of static electricity to the composite material, after the carbon nanotubes are introduced into the polyester to form a nano composite material, the conductive network is formed in the system, and the resistance value of the polymer substrate is lowered due to the carbon nanometer. The mutual contact between the tubes allows electrons to be rapidly transferred from the conjugated electrons on the surface of the carbon nanotubes, and the excess charge can be released, giving the composite an antistatic effect.
在奈米複合材中，碳管與碳管之間並未接觸或直接接觸，其之間的距離小到某一個範圍內，這種未接觸可會有導電現象，稱之為穿遂效應(tunnel effect)。由表4所示，奈米複合材料表面電阻隨著碳管含量增加而下降，即導電性會提高。而添加0.5 wt%之原始奈米碳管(u-CNT)時，奈米複合材料表面電阻為1.68×107 Ω/cm2 ，較純聚酯的表面電阻(5.30×1012 Ω/cm2 )低，顯示添加奈米碳管會增加複合材料的導電性質，而添加0.5 wt%改質碳管CNT-18的複合材料，其表面電阻為7.82×105 Ω/cm2 ，比聚酯和原始碳管PC複合材料的表面電阻降低許多，主要是因為有機改質奈米碳管CNT-18較原始奈米碳管u-CNT不易產生聚集糾結的情形，並可以均勻的分散在聚酯高分子中，因而較易形成導電網路。而添加酯交換劑至改質奈米碳管與聚酯複合材料中，其表面電阻增加為4.84×1012 Ω/cm2 ，發現比原始與改質奈米碳管之複合材料來的高，可能原因是由於碳管與聚酯嫁接後，導致其導電性受到影響，但仍比聚酯的表面電阻來的低。而當添加1.5 wt%改質碳管奈米碳管複合材，其表面電阻為9.30×104 Ω/cm2 ，比添加酯交換劑與原始碳管之複合材來的低，表示經由十八烷醇改質碳管之奈米複合材，其均勻地分散於聚酯中，可使碳管和碳管之間容易接觸或產生隧道效應，而使複合材料所需添加碳管量的導電門檻降低。從表面電阻變化的趨勢發現，隨著改質碳管含量增加會使表面電阻降低且較原始碳管複合材料下降的多，而添加3 wt%改質奈米碳管以及再添加酯交換劑的兩種複合材料，其表面電阻降低至10-1 Ω/cm2 以下，已經非常有效降低複合材料的電阻。而同樣含3 wt%碳管之PC-18T複合材料，其電阻較PC-18複合材料低，顯示添加酯交換劑，可使碳管與聚酯之結合力增強，使分散更均勻穩定，因此在高碳管含量下，呈現較佳的導電性質及機械性質。In the nanocomposite, there is no contact or direct contact between the carbon tube and the carbon tube, and the distance between them is small to a certain range. This non-contact may have a conductive phenomenon, which is called a piercing effect ( Tunnel effect). As shown in Table 4, the surface resistance of the nanocomposite decreases as the carbon tube content increases, that is, the conductivity increases. When 0.5 wt% of the original carbon nanotubes (u-CNT) were added, the surface resistance of the nanocomposite was 1.68 × 10 7 Ω/cm 2 , which was lower than that of the pure polyester (5.30 × 10 12 Ω/cm 2 ). Low, indicating that the addition of carbon nanotubes will increase the conductive properties of the composite, while the composite with 0.5 wt% modified carbon nanotubes CNT-18 has a surface resistance of 7.82×10 5 Ω/cm 2 , which is better than polyester and The surface resistance of the original carbon tube PC composites is much lower, mainly because the organically modified carbon nanotubes CNT-18 are less prone to aggregation and entanglement than the original carbon nanotubes, and can be uniformly dispersed in the polyester. In the molecule, it is thus easier to form a conductive network. When the ester exchanger was added to the modified carbon nanotube and polyester composite, the surface resistance increased to 4.84×10 12 Ω/cm 2 , which was found to be higher than that of the composite material of the original and modified carbon nanotubes. The possible reason is that the conductivity of the carbon tube is affected by the grafting of the polyester, but it is still lower than the surface resistance of the polyester. When the 1.5 wt% modified carbon nanotube carbon nanotube composite is added, the surface resistance is 9.30×10 4 Ω/cm 2 , which is lower than that of the composite of the ester exchanger and the original carbon tube. The nanocomposite of the alkanol-modified carbon tube is uniformly dispersed in the polyester, so that the carbon tube and the carbon tube can be easily contacted or tunneled, and the conductive threshold of the carbon tube amount required for the composite material is required. reduce. From the trend of surface resistance change, it is found that the surface resistance decreases with the increase of the modified carbon tube content and decreases more than that of the original carbon tube composite, while the addition of 3 wt% modified carbon nanotubes and the addition of transesterification agent are added. Two composite materials whose surface resistance is reduced to 10 -1 Ω/cm 2 or less have been very effective in reducing the electrical resistance of the composite. The PC-18T composite material with the same 3 wt% carbon tube has lower electrical resistance than the PC-18 composite material, indicating that the addition of the transesterification agent can enhance the bonding force between the carbon tube and the polyester, and make the dispersion more uniform and stable. At high carbon tube content, it exhibits better electrical and mechanical properties.
一般材料的表面電阻介於109 至1012 Ω/cm2 就具有抗靜電(anti-static)的功效，而105 至109 Ω/cm2 為靜電消散等級(electrostatic discharge,ESD)，<105 Ω/cm2 其具有ESD傳導功能，而<1 Ω/cm2 則有電磁波遮蔽效果。本研究發現當奈米碳管的添加量超過0.5 wt%時，PC、PC-18、PC-18T三系列複合材料就可達抗靜電的效果，其可以應用於電子工業或電子包裝材之產業。Generally, the surface resistance of the material is 10 9 to 10 12 Ω/cm 2 , which has an anti-static effect, and 10 5 to 10 9 Ω/cm 2 is an electrostatic discharge (ESD). 10 5 Ω/cm 2 has an ESD conduction function, and <1 Ω/cm 2 has an electromagnetic wave shielding effect. This study found that when the amount of carbon nanotubes added exceeds 0.5 wt%, PC, PC-18, PC-18T three series of composite materials can achieve antistatic effect, which can be applied to the electronics industry or electronic packaging industry. .
請參見表5所示，藉由電磁波遮蔽效率分析，聚酯/奈米碳管複合材料：PC-18與PC-18T，各材料於不同電場下，發現當加入酯交換劑(PC-18T 3%)後，其在各頻率下之電磁波遮蔽效率都較未加入酯交換劑之材料(PC-18 3%)為佳。See Table 5, by electromagnetic wave shielding efficiency analysis, polyester/nanocarbon tube composites: PC-18 and PC-18T, each material under different electric fields, found when adding transesterification agent (PC-18T 3 After %), the electromagnetic wave shielding efficiency at each frequency is better than that of the material without the ester exchanger (PC-18 3%).
圖1係為本發明含奈米碳管與聚酯之複合材料之製造流程圖。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the manufacture of a composite material comprising a carbon nanotube and a polyester according to the present invention.
附件1為本發明含奈米碳管與聚酯之複合材料之製造流程示意圖。Annex 1 is a schematic diagram of the manufacturing process of the composite material containing the carbon nanotubes and the polyester of the present invention.
附件2為本發明添加有酯交換劑的含奈米碳管與聚酯之複合材料之製造流程示意圖。Attachment 2 is a schematic view showing the manufacturing process of a composite material comprising a carbon nanotube and a polyester to which an ester exchanger is added.
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