TWI398472B - Polymer composite material and its manufacturing method - Google Patents
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本發明是有關於一種高分子複合材料及其製造方法，特別是有關含有改質碳奈米管之高分子複合材料及其製造方法。 The present invention relates to a polymer composite material and a method for producing the same, and more particularly to a polymer composite material containing a modified carbon nanotube and a method for producing the same.
碳奈米管(carbon nanotube,CNT)係約十年前由日本S.Ijima所發現，由於碳奈米管具有特殊的性質，包括低密度、高強度、高韌性、可撓曲、高表面積、表面曲度大，以及具有獨特的電學性質與極佳的導電性和傳熱性，所以吸引許多研究工作者專注於開發其可能的應用方式，例如複合材料、微電子材料、平面顯示器、無線通訊、燃料電池、鋰離子電池等。石墨被認為是半導體金屬材料，而與石墨一樣由碳原子所構成之碳奈米管則依其對稱性可分成半導體及導體的性質，若碳奈米管能分散於高分子基材中，應能補強高分子缺乏機械強度與耐熱性質的缺點。 Carbon nanotube (CNT) was discovered by S. Ijima of Japan about a decade ago. Due to its special properties, carbon nanotubes include low density, high strength, high toughness, flexibility, and high surface area. The large curvature of the surface, as well as its unique electrical properties and excellent electrical and thermal conductivity, has attracted many researchers to focus on developing possible applications such as composites, microelectronics, flat panel displays, wireless communications. , fuel cells, lithium-ion batteries, etc. Graphite is considered to be a semiconducting metal material, and a carbon nanotube composed of carbon atoms like graphite can be classified into a semiconductor and a conductor according to its symmetry. If the carbon nanotube can be dispersed in a polymer substrate, The reinforcing polymer has the disadvantages of lack of mechanical strength and heat resistance.
導電性高分子材料之用途，依照不同之電阻需求，主要包括四部份：第一為抗靜電材料；第二為靜電放電(electro-static discharge,ESD)防護；第三為電磁波/無線電波(electromagnetic interference/radio frequency interference,EMI/RFI)遮蔽；第四為導電接著部份。因此，直接在高分子中做導電改質，如聚苯胺(polyaniline)等、或添加導電性填充劑，如導電碳黑或金屬粉末，以增加高分子材料避免電荷聚集或轉移電荷的能力期限。如下表一 所示之導電性高分子材料之用途分類。 The use of conductive polymer materials, according to different resistance requirements, mainly includes four parts: the first is antistatic material; the second is electrostatic-static discharge (ESD) protection; the third is electromagnetic wave/radio wave ( The electromagnetic interference/radio frequency interference (EMI/RFI) is shielded; the fourth is the conductive follow-up portion. Therefore, conductive modification directly in the polymer, such as polyaniline, or the addition of conductive fillers, such as conductive carbon black or metal powder, to increase the ability of the polymer material to avoid charge accumulation or transfer charge. As shown in Table 1 below The use classification of the conductive polymer materials shown.
然而，先前技術將純碳奈米管添加入一般高分子複合材料(如聚烯烴高分子材料)內時，僅靠些微的凡得瓦爾力使其混合於其中，而導致所產生之界面物性問題，如材料彎曲強度不足及電路導通不佳等問題無法克服。此外，碳奈米管為十分昂貴的材料，其販售時以公克為單位，在高分子複合材料中添加碳奈米管亦會增加成本。因此，如何克服上述的材料介面物性問題，以製造出含碳奈米管之高分子複合材料，同時降低碳奈米管的用量且可達到想要的功效，是一個極待解決的問題。 However, in the prior art, when a pure carbon nanotube is added to a general polymer composite material (such as a polyolefin polymer material), only a slight van der Waals force is mixed therein, resulting in an interface physical property problem. Problems such as insufficient bending strength of the material and poor circuit conduction cannot be overcome. In addition, carbon nanotubes are very expensive materials, which are sold in grams, and the addition of carbon nanotubes to polymer composites also increases costs. Therefore, how to overcome the above-mentioned material interface physical property problem to manufacture a polymer composite material containing carbon nanotubes, and reduce the amount of carbon nanotubes and achieve the desired effect is an extremely problem to be solved.
有鑑於此，本發明之目的就是在提供一種含改質碳奈米管的高分子複合材料及其製造方法，以達到僅需較低用量的碳奈米管，即可使碳奈米管很均勻的分散在高分子基材中，進而增加高分子的機械強度與耐熱性質。 In view of the above, the object of the present invention is to provide a polymer composite material containing a modified carbon nanotube and a manufacturing method thereof, so as to achieve a carbon nanotube with only a small amount of carbon nanotubes, the carbon nanotube tube can be made very It is uniformly dispersed in the polymer substrate, thereby increasing the mechanical strength and heat resistance of the polymer.
此含碳奈米管的高分子複合材料能產生共價鍵結及氫鍵的效益，得以克服往常所使用的複合材料會與純碳奈米 管作用時，所產生之界面物性問題如材料彎曲強度不足及電路導通不佳之問題。 The carbon nanotube-containing polymer composite material can produce covalent bonding and hydrogen bonding benefits, thereby overcoming the conventionally used composite materials and pure carbon nanotubes. When the tube acts, the resulting physical properties of the interface are such as insufficient bending strength of the material and poor conduction of the circuit.
根據本發明之目的，提出一種高分子複合材料之製造方法，其步驟包括先將碳奈米管均勻分散於有機溶劑中，再將具有至少三個碳-碳雙鍵官能基之不飽和單體及自由基起始劑加入上述有機溶劑中，使其藉由自由基起始劑之活化反應，而使具有至少三個碳-碳雙鍵官能基之不飽和單體共價鍵結於碳奈米管上，以取得改質碳奈米管。將所獲得乾燥後之改質碳奈米管，與聚烯烴高分子置入一捏合用、掺合用或混合用之機器中進行混練，即製得本發明之高分子複合材料。 According to the object of the present invention, a method for manufacturing a polymer composite material is provided, the steps comprising uniformly dispersing a carbon nanotube tube in an organic solvent, and then unsaturated monomers having at least three carbon-carbon double bond functional groups. And a radical initiator is added to the above organic solvent to cause an unsaturated monomer having at least three carbon-carbon double bond functional groups to be covalently bonded to carbon naphthalene by an activation reaction of a radical initiator On the rice tube, to obtain a modified carbon nanotube. The obtained modified carbon nanotube tube is kneaded with a polyolefin polymer in a machine for kneading, blending or mixing to obtain the polymer composite material of the present invention.
根據本發明之目的，提出一種高分子複合材料，其係由上述製造方法所製備得，其包括聚烯烴高分子，以及均勻分散於此聚烯烴高分子中的改質碳奈米管。 In accordance with the purpose of the present invention, a polymer composite material is prepared which is prepared by the above-described manufacturing method and which comprises a polyolefin polymer and a modified carbon nanotube uniformly dispersed in the polyolefin polymer.
承上所述，依本發明之高分子複合材料及其製造方法，其可具有一或多個下述優點： As described above, the polymer composite material and the method of manufacturing the same according to the present invention may have one or more of the following advantages:
(1)本發明之高分子複合材料，其在電氣性質、機械性質、熱性質和磁性質方面，係展現出低比重、高強度、高韌性、極大的表面能及彎曲延展性，且具有高的化學安定性。 (1) The polymer composite material of the present invention exhibits low specific gravity, high strength, high toughness, great surface energy and bending ductility in terms of electrical properties, mechanical properties, thermal properties and magnetic properties, and has high Chemical stability.
(2)本發明所製得之改質碳奈米管係具有較佳之材料分散性，可以較低的用量即達到顯著改善融合後所得之高分子複合材料的機械性質及電氣性質。 (2) The modified carbon nanotube tube obtained by the invention has better material dispersibility, and can achieve a significant improvement in the mechanical properties and electrical properties of the polymer composite material obtained after the fusion.
以下將參照相關圖式，說明依本發明較佳實施例之高分子複合材料及其製備方法。 Hereinafter, a polymer composite material according to a preferred embodiment of the present invention and a method for preparing the same will be described with reference to the related drawings.
本發明中所述之「碳奈米管」一詞，除了表示碳奈米管之外，亦包含碳奈米線(carbon nanowires)、碳奈米纖維或碳奈米球。碳奈米管的製造技術一般多用化學氣相沉積(CVD)，其已經為業界所習知，並且在市場上已有商品化碳奈米管在販售。於本發明之實施例中係購買商品化之碳奈米管直接使用。 The term "carbon nanotube" as used in the present invention includes carbon nanowires, carbon nanofibers or carbon nanospheres in addition to carbon nanotubes. Carbon nanotubes are generally manufactured using chemical vapor deposition (CVD), which is well known in the art and commercially available carbon nanotubes are on the market. In the embodiment of the present invention, a commercially available carbon nanotube is purchased for direct use.
請參閱第1圖，其係為本發明之高分子複合材料之製造方法之步驟流程圖。其步驟可包括：步驟S11，將未經改質之碳奈米管分散於有機溶劑中。步驟S12，加入具有至少三個碳-碳雙鍵官能基之不飽和單體及自由基起始劑於上述含有碳奈米管之有機溶劑中，使其進行反應，而使上述不飽和單體接枝於碳奈米管，即取得一改質碳奈米管，以及步驟S13，將此改質碳奈米管與聚烯烴高分子置於一捏合用、掺合用或混合用之機器進行混練，以取得高分子複合材料。 Please refer to FIG. 1 , which is a flow chart of the steps of the method for producing the polymer composite material of the present invention. The step may include: in step S11, dispersing the unmodified carbon nanotube in an organic solvent. Step S12, adding an unsaturated monomer having at least three carbon-carbon double bond functional groups and a radical initiator to the above organic solvent containing a carbon nanotube to cause a reaction to obtain the above unsaturated monomer Grafting to the carbon nanotube tube, that is, obtaining a modified carbon nanotube tube, and step S13, placing the modified carbon nanotube tube and the polyolefin polymer in a kneading, blending or mixing machine for kneading To obtain polymer composite materials.
其中，碳奈米管可包括單壁碳奈米管及多壁碳奈米管(multi-wall cabon nanotubes,MWNTs)，而聚烯烴高分子可包括聚乙烯(PE)、聚丙烯(PP)或聚乙烯烴彈性體(POE)，且改質碳奈米管對聚烯烴高分子之重量比較佳係為0.1%至5.0%。 The carbon nanotubes may include single-walled carbon nanotubes and multi-wall cabon nanotubes (MWNTs), and the polyolefin polymer may include polyethylene (PE), polypropylene (PP) or The polyethylene hydrocarbon elastomer (POE), and the modified carbon nanotubes preferably have a weight of the polyolefin polymer of 0.1% to 5.0%.
所選用具有至少三個碳-碳雙鍵官能基之不飽和單體可包括三聚氰酸三烯丙酯(triallyl isocyanurate, TAIC)、三羥甲基丙烷三丙烯酸酯(trimethylolpropane triacrylate,TMPTA)、季戊四醇三丙烯酸酯(pentaerythritol triacrylate,PETRA)、乙氧化三羥甲基丙烷三丙烯酸酯(ethoxylated trimethylolpropane triacrylate,3EOTMPTA)、丙氧化甘油三丙烯酸酯(propoxylated glycerol triacrylate,POGTA)、三丙烯醯氧乙基磷酸酯(tris-Acryloyloxyethyl phosphate,TAOEP)、或季戊四醇四丙烯酸酯(pentaerythritol tetraacrylate,PETEA)。 The unsaturated monomer selected to have at least three carbon-carbon double bond functional groups may include triallyl isocyanurate, TAIC), trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETRA), ethoxylated trimethylolpropane triacrylate (3EOTMPTA), glycerol oxide Propoxylated glycerol triacrylate (POGTA), tris-Acryloyloxyethyl phosphate (TAOEP), or pentaerythritol tetraacrylate (PETEA).
所使用的有機溶劑可包括丙酮、四氫呋喃(tetrahydrofuran,THF)、N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidone,NMP)、N,N-二甲基乙醯胺(,N,N-dimethylacetamide；DMAc)、二甲基甲醯胺(dimethylformamide,DMF)、二甲亞碸(dimethylsulfoxide,DMSO)、m-甲酚(m-cresol)、氯化甲烷、氯化乙烷、苯、二甲苯或氯苯。自由基起始劑則可包括偶氮化合物或過氧化物，其中過氧化物可包括過氧化苯甲醯(benzoyl peroxisde,BPO)或過氧化二異丙苯(dicumyl peroxide,DCP)。 The organic solvent to be used may include acetone, tetrahydrofuran (THF), N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (N, N, N-dimethylacetamide; DMAc), dimethylformamide (DMF), dimethylsulfoxide (DMSO), m-cresol, methane chloride, ethane chloride, benzene, Xylene or chlorobenzene. The free radical initiator may then comprise an azo compound or a peroxide, wherein the peroxide may comprise benzoyl peroxisde (BPO) or dicumyl peroxide (DCP).
此外，本發明之高分子複合材料之製造方法視需要更可提供纖維補強材料、無機填料或有機填料，使其與改質碳奈米管及聚烯烴高分子混合。此纖維補強材料可為天然的植物纖維(例如亞麻纖維或竹炭纖維)或無機纖維(例如玻璃纖維或碳纖維)。 Further, the method for producing the polymer composite material of the present invention may further provide a fiber reinforcing material, an inorganic filler or an organic filler to be mixed with the modified carbon nanotube and the polyolefin polymer as needed. The fiber reinforcing material may be a natural plant fiber (for example, flax fiber or bamboo charcoal fiber) or an inorganic fiber (for example, glass fiber or carbon fiber).
其中，上述機器係為布斯混合器、萬馬力混合器、雙螺桿押出機、加壓混合器、熱壓機、反應槽或塑譜儀等混練器具。另外，其製造方法視需要可包含一製粒步驟，製粒步驟係跟據目的物而選用押出成型、射出成型、熱壓成型、中空成型或發泡成型之加工程序，來製成具有實用形式的高濃度母粒或成型品。 The above-mentioned machine is a kneading device such as a Buss mixer, a 10,000-mass mixer, a twin-screw extruder, a pressure mixer, a hot press, a reaction tank or a spectrometer. In addition, the manufacturing method may include a granulation step as needed, and the granulation step is carried out in a practical form by using a processing procedure of extrusion molding, injection molding, hot press molding, hollow molding or foam molding according to the object. High concentration of masterbatch or molded product.
請參閱第2圖，其係為本發明之高分子複合材料之一實施例之化學結構圖。在此實施例中，其未經改質之碳奈米管係以多壁碳奈米管來實施，所選用之有機溶劑為丙酮，自由基起始劑則使用過氧化苯甲醯(BPO)，具有至少三個碳-碳雙鍵官能基之不飽和單體係以三聚氰酸三烯丙酯(TAIC)來實施，而所選用之聚烯烴高分子則以聚乙烯來實施。圖中，此改質碳奈米管的製造方式係為：首先將1.5克未經改質之碳奈米管分散於300毫升的丙酮中，再經由超音波震盪約90分鐘使碳奈米管能均勻分散於丙酮中。震盪完後，加入包括過氧化苯甲醯與聚乙烯之改質劑，並使其於加熱攪拌器中溫度80℃下攪拌4小時，使自由基起始劑能完整的反應。之後過濾時，反覆的過濾3至4次以去除殘餘之自由基起始劑。清洗完畢後再使用真空烘箱以65℃烘烤24小時，以去除殘留的水分，即得到改質碳奈米管(以下係以TAIC-g-CNT表示)。接著，將改質碳奈米管依各種比例(分別為0,0.5,1,2,4 wt%)秤量所需的含量，並利用塑譜儀使其與聚乙烯作混練，即製得碳奈米管/聚乙烯複合材料(以下係以TAIC-g-CNT/PE複合材料表示)。其係將不同比例改質碳 奈米管與聚乙烯之分別置入螺桿溫度1650℃之塑譜儀(Brabender)中均勻攪拌5分鐘，之後再到熱壓機成壓成長125mm、寬110mm且厚3mm的試片，其熱壓機溫度為1650℃，熱壓時間200秒。且試片利用線切機裁成寬13mm的試片，以便做機械性質測試。 Please refer to Fig. 2, which is a chemical structural diagram of an embodiment of the polymer composite material of the present invention. In this embodiment, the unmodified carbon nanotube tube is implemented as a multi-walled carbon nanotube, the selected organic solvent is acetone, and the radical initiator is benzoic acid peroxide (BPO). An unsaturated single system having at least three carbon-carbon double bond functional groups is carried out with triallyl cyanurate (TAIC), and the selected polyolefin polymer is carried out with polyethylene. In the figure, the modified carbon nanotube is manufactured by first dispersing 1.5 g of unmodified carbon nanotubes in 300 ml of acetone, and then oscillating by ultrasonic waves for about 90 minutes to make carbon nanotubes. Can be evenly dispersed in acetone. After the shaking, a modifier including benzammonium peroxide and polyethylene was added, and the mixture was stirred at a temperature of 80 ° C for 4 hours in a heating stirrer to allow the radical initiator to be completely reacted. After filtration, the filtration was repeated 3 to 4 times to remove residual free radical initiator. After the cleaning was completed, it was baked at 65 ° C for 24 hours using a vacuum oven to remove residual moisture, thereby obtaining a modified carbon nanotube (hereinafter referred to as TAIC-g-CNT). Next, the modified carbon nanotubes are weighed in various proportions (0, 0.5, 1, 2, 4 wt%, respectively), and mixed with polyethylene by a spectrometer to obtain carbon. Nanotube/polyethylene composite (hereinafter referred to as TAIC-g-CNT/PE composite). It will change carbon in different proportions. The nanotubes and the polyethylene were respectively placed in a fiber spectrometer (Brabender) with a screw temperature of 1,650 ° C for 5 minutes, and then heated to a hot press to grow a test piece of 125 mm, a width of 110 mm and a thickness of 3 mm. The machine temperature was 1650 ° C and the hot pressing time was 200 seconds. The test piece was cut into a test piece having a width of 13 mm by a wire cutter to perform a mechanical property test.
本發明所提供之具有至少三個碳-碳雙鍵官能基之不飽和單體與未改質碳奈米管之反應，因立體障礙關係，不飽和單體僅有部分的碳-碳雙鍵官能基會與碳奈米管表面的碳-碳雙鍵官能基起共價鍵結(covalent bond)反應。所以經改質的碳奈米管仍含有未反應之碳-碳雙鍵官能基，可與聚烯烴高分子的碳-碳雙鍵官能基產生共價鍵結(covalent bond)，其中，共價鍵之作用力約為50~200 Kcal/mole，係大於凡得瓦爾力(0.5~2 Kcal/mole)。因此，此經改質之碳奈米管在聚烯烴高分子中有較好的分散性，可提升高分子複合材料之電氣性質及機械性質。 The reaction of the unsaturated monomer having at least three carbon-carbon double bond functional groups provided by the invention and the unmodified carbon nanotubes has only a part of carbon-carbon double bonds in the unsaturated monomer due to steric hindrance The functional group will react with the carbon-carbon double bond functional group on the surface of the carbon nanotube to covalent bond. Therefore, the modified carbon nanotube still contains an unreacted carbon-carbon double bond functional group, and can generate a covalent bond with the carbon-carbon double bond functional group of the polyolefin polymer, wherein the covalent bond The force of the bond is about 50~200 Kcal/mole, which is greater than the van der Waals force (0.5~2 Kcal/mole). Therefore, the modified carbon nanotube has good dispersibility in the polyolefin polymer, and can improve the electrical properties and mechanical properties of the polymer composite.
機械性質檢測為檢定材料各種機械強度的依據，在探討中，可分為抗拉性質(tensile property)、耐衝擊強度(impact strength)及熱變形溫度(heat deflection temperature,HDT)。為了探討本發明之改質碳奈米管在混合聚乙烯過程中，在不同成分的組成下，比較各組的機械性質，探討出是否添加改質碳奈米管含量越多，就會越提升高分子複合材料的機械性質。此外，亦探討改質碳奈米管的添加含量對其所製得之高分子複合材料的熱性質與電氣性質亦為何。本發明之一 實施例係以第2圖所製得之TAIC-g-CNT/PE作為實驗組；且係以添加未改質的碳奈米管於聚乙烯中進行混練所製得之高分子複合材料(以下係以CNT/PE複合材料表示)作為控制組；而添加以馬來酸酐(maleic anhydride,MA)進行表面改質之另一改質碳奈米管於聚乙烯中，進行混練所製得之高分子複合材料(以下係以MA-g-CNT/PE複合材料表示)作為對照組。其實驗結果如下所示： Mechanical properties are the basis for the verification of various mechanical strengths of materials. In the discussion, they can be divided into tensile properties, impact strength and heat deflection temperature (HDT). In order to investigate the modified carbon nanotubes of the present invention, in the process of mixing polyethylene, the mechanical properties of each group are compared under the composition of different components, and it is found that the more the modified carbon nanotubes are added, the more the carbon nanotubes are added. The mechanical properties of polymer composites. In addition, the thermal and electrical properties of the polymer composites prepared by the modified carbon nanotubes are also discussed. One of the inventions The examples are TAIC-g-CNT/PE prepared in Fig. 2 as an experimental group; and the polymer composite material obtained by mixing unmodified carbon nanotubes in polyethylene (hereinafter It is represented by CNT/PE composite material as a control group; and another modified carbon nanotube tube modified with maleic anhydride (MA) is added to polyethylene and mixed by polyethylene. Molecular composite materials (hereinafter referred to as MA-g-CNT/PE composite materials) were used as a control group. The experimental results are as follows:
請參閱第3圖，其係為上述各高分子複合材料(實驗組、控制組及對照組)之熱變形溫度對碳奈米管含量之曲線圖。由圖中可觀察到，隨著碳奈米管含量的增加，耐熱性也相對的增加。其中，CNT/PE複合材料於碳奈米管含量為0wt%時的熱變形溫度為67.9℃，與其含量為4wt%時的熱變形溫度72.5℃相差了4.6℃，可知碳奈米管只需加少許的含量，其熱變形溫度即可有很明顯的增加。而以改質劑改質過的MA-g-CNT/PE複合材料與TAIC-g-CNT/PE複合材料和未改質的CNT/PE複合材料做比較，可發現經過MA改質過之MA-g-CNT/PE複合材料的熱變形溫度係由69.2℃增加72.9℃(增加3.7℃)，相同的經過TAIC改質過的之TAIC-g-CNT/PE複合材料的熱變形溫度則由70.9℃增加75.1℃(增加4.2℃)。此結果可以知道經過TAIC改質的碳奈米管，因其網狀交聯的結構，在熱變形溫度上具有較佳的提升效果。 Please refer to FIG. 3, which is a graph of the heat distortion temperature versus the carbon nanotube content of each of the above polymer composite materials (experimental group, control group, and control group). It can be observed from the figure that as the carbon nanotube content increases, the heat resistance also increases relatively. Among them, the CNT/PE composite material has a heat distortion temperature of 67.9 ° C when the carbon nanotube content is 0 wt%, and a heat distortion temperature of 72.5 ° C when the content is 4 wt%, which is 4.6 ° C, which means that the carbon nanotube tube only needs to be added. With a small amount, the heat distortion temperature can be significantly increased. Compared with TAIC-g-CNT/PE composites and unmodified CNT/PE composites, MA-g-CNT/PE composites modified with modifiers can be found in MA modified by MA. The heat distortion temperature of the -g-CNT/PE composite increased by 72.9 °C (by 3.7 °C) from 69.2 °C, and the thermal deformation temperature of the same TAIC-g-CNT/PE composite modified by TAIC was 70.9. °C increased by 75.1 ° C (increase 4.2 ° C). This result shows that the carbon nanotube modified by TAIC has a better lifting effect at the heat distortion temperature due to its network crosslinked structure.
請參閱第4圖，其係為上述各高分子複合材料(實驗組、控制組及對照組)之拉伸強度對碳奈米管含量之曲線圖。本發明之抗拉性質測試，係使用Instron萬能試驗機，依 ASTM規範進行拉伸(ASTM D638,50 mm/min)。圖中，可得知添加經過改質的碳奈米管所製得之高分子複合材料在拉伸強度上有明顯的改變，且隨碳奈米管含量的增加抗拉性質也跟著增加。其中，未改質的CNT/PE複合材料可從碳奈米管含量0wt%的78.8kg升至4wt%的85.8kg(增加108%)。而經改質的碳奈米管與未改質的碳奈米管相比較上，含有改質過的碳奈米管之MA-g-CNT/PE複合材料與TAIC-g-CNT/PE複合材料，在碳奈米管含量0.5wt%~2wt%的拉伸強度相對的比未改質的抗拉強度來的高。而以碳奈米管含量2wt%來看，未改質的CNT/PE複合材料為83.6kg，與改質過的TAIC-g-CNT複合材料之86.9kg相差了3.3kg。此結果是由於碳奈米管在高密度的聚乙烯(HDPE)中有較佳的分散之故，也就是碳奈米管均勻分散的結果使得與聚乙烯基材之間有良好的界面。當基材與纖維之間若沒有良好的界面時，通常複合材料的拉伸強度會隨著纖維含量的增加而顯著的下降。為了使碳奈米管與基材間具有化學鍵結或物理鍵結，本發明係利用自由基反應的方式將TAIC接枝到碳奈米管上(TAIC-g-CNT)，使與基材(PE-g-TAIC)間產生相容的效益，而能改善基材與碳奈米管之間的界面，得以大幅提昇TAIC-g-CNT/PE複合材料之物性。因此，本發明經改質的碳奈米管(TAIC-g-CNT)可增加了與高分子複合材料的相容性，且此經改質的碳奈米管與高分子複合材料之間有較強的共價鍵結或引力的存在，可有效提升此高分子複合材料物性之拉伸強度。 Please refer to Fig. 4, which is a graph of tensile strength versus carbon nanotube content of each of the above polymer composite materials (experimental group, control group, and control group). The tensile property test of the present invention is performed by using an Instron universal testing machine. The ASTM specification is stretched (ASTM D638, 50 mm/min). In the figure, it can be seen that the polymer composite material obtained by adding the modified carbon nanotube tube has a significant change in tensile strength, and the tensile property increases with the increase of the carbon nanotube content. Among them, the unmodified CNT/PE composite material can be increased from 78.8 kg of carbon nanotube content of 0 wt% to 85.8 kg (by 108%) of 4 wt%. Compared with the unmodified carbon nanotubes, the modified carbon nanotubes and the MA-g-CNT/PE composites with modified carbon nanotubes are combined with TAIC-g-CNT/PE. The tensile strength of the material at a carbon nanotube content of 0.5 wt% to 2 wt% is relatively higher than that of the unmodified tensile strength. According to the carbon nanotube content of 2wt%, the unmodified CNT/PE composite material was 83.6kg, which was 3.3kg different from the modified 86.9kg of TAIC-g-CNT composite material. This result is due to the better dispersion of the carbon nanotubes in the high density polyethylene (HDPE), that is, the uniform dispersion of the carbon nanotubes results in a good interface with the polyethylene substrate. When there is no good interface between the substrate and the fiber, the tensile strength of the composite generally decreases significantly as the fiber content increases. In order to chemically bond or physically bond the carbon nanotubes to the substrate, the present invention utilizes a free radical reaction to graft TAIC onto a carbon nanotube (TAIC-g-CNT) to make a substrate ( The compatibility between PE-g-TAIC) and the interface between the substrate and the carbon nanotubes can greatly improve the physical properties of the TAIC-g-CNT/PE composite. Therefore, the modified carbon nanotube (TAIC-g-CNT) of the present invention can increase the compatibility with the polymer composite, and there is a relationship between the modified carbon nanotube and the polymer composite. The presence of strong covalent bonding or gravitation can effectively increase the tensile strength of the physical properties of the polymer composite.
請參閱第5圖，其係為上述各高分子複合材料(實驗組、控制組及對照組)之缺口耐衝擊強度對碳奈米管含量之曲線圖。本發明之耐衝擊試驗，係以艾式缺口耐衝擊強度(Notched Izod Impactstrength)來實施。由此圖可得知，碳奈米管的增加在衝擊強度上會有減弱的趨勢，然經過改質的碳奈米管在衝擊上都比未改質的好，而相對的碳奈米管含量的增加，衝擊強度也是有下降的趨勢。碳奈米管含量0.5 wt%的未經改質的CNT/PE複合材料和改質過的MA-g-CNT/PE複合材料相比較，衝擊值可由0.19 J/M上升到0.31 J/M，可知改質過的碳奈米管在0.5 wt%的衝擊值最大。而網狀交聯之TAIC-g-CNT/PE複合材料對衝擊強度仍較未經改質的CNT/PE複合材料來的好。 Please refer to FIG. 5, which is a graph showing the notched impact strength versus the carbon nanotube content of each of the above polymer composite materials (experimental group, control group, and control group). The impact resistance test of the present invention is carried out by Notched Izod Impact strength. It can be seen from this figure that the increase of carbon nanotubes tends to decrease in impact strength, but the modified carbon nanotubes are better in impact than unmodified, while the opposite carbon nanotubes As the content increases, the impact strength also tends to decrease. The impact value of the unmodified CNT/PE composite with a carbon nanotube content of 0.5 wt% can be increased from 0.19 J/M to 0.31 J/M compared to the modified MA-g-CNT/PE composite. It can be seen that the modified carbon nanotube has the largest impact value at 0.5 wt%. The mesh crosslinked TAIC-g-CNT/PE composite is better for impact strength than the unmodified CNT/PE composite.
請參閱第6及7圖，其係分別為上述各高分子複合材料(實驗組、控制組及對照組)之熱重分析儀(TGA)微分曲線圖與TGA最大熱裂解圖。圖中顯示碳奈米管比例的增加可以提高聚乙烯在熱重損失方面的溫度。但是經過改質的碳奈米管在熱裂解溫度的表現並沒有與未改質的好，相對的未改質的碳奈米管含量在0wt%之469.12℃到含量4wt%之499.36℃之中增加了30℃，由此可知碳奈米管只需加入少許的含量，在基材中可以提升基材的耐熱溫度，而改質過的碳奈米管表面在高溫時表面的改質劑會先被裂解掉而導致耐熱溫度下降，且結果顯示改質過的碳奈米管在熱裂解溫度中以TAIC的系統在低碳奈米管含量時表現最好，顯示網狀結構有助於複合材料耐熱性質的提昇 。 Please refer to Figures 6 and 7 for the thermogravimetric analyzer (TGA) differential curve and TGA maximum pyrolysis chart of each of the above polymer composite materials (experimental group, control group and control group). The figure shows that an increase in the proportion of carbon nanotubes can increase the temperature of the polyethylene in terms of thermogravimetric loss. However, the performance of the modified carbon nanotubes at the thermal cracking temperature is not as good as that of the unmodified ones. The relative unmodified carbon nanotubes content is between 469.12 ° C of 0 wt% and 499.36 ° C of 4 wt%. The addition of 30 ° C, it can be known that the carbon nanotubes only need to add a small amount, in the substrate can raise the heat resistance temperature of the substrate, and the surface of the modified carbon nanotube surface at high temperature will be modified It was first cleaved to cause a decrease in the heat-resistant temperature, and the results showed that the modified carbon nanotubes performed best at the low-carbon nanotube content in the TAIC system at the thermal cracking temperature, indicating that the network structure contributes to the composite. Improvement of heat resistance of materials .
請參閱第8圖，其係為上述各高分子複合材料(實驗組、控制組及對照組)之示差熱分析儀(DSC)曲線圖。DSC分析主要是在測定高密度聚乙烯和改質過的多壁碳奈米管之間的相容性，並瞭解多壁碳奈米管對高密度聚乙烯結晶性質的影響。圖中為2wt%的碳奈米管，由圖中可以得知碳奈米管增加對於軟化溫度與融點溫度並沒有提升的效果。經過改質與未改質的碳奈米管的融點溫度在127℃~130℃之間，所以顯示未改質碳奈米管與改質碳奈米管在DSC(Differential Scanning Calorimeter)中並沒有多大的改變，只能略微提昇聚乙烯的結晶溫度。 Please refer to FIG. 8 , which is a differential thermal analyzer (DSC) graph of each of the above polymer composite materials (experimental group, control group, and control group). DSC analysis is mainly to determine the compatibility between high density polyethylene and modified multi-wall carbon nanotubes, and to understand the effect of multi-wall carbon nanotubes on the crystalline properties of high density polyethylene. In the figure, it is a 2wt% carbon nanotube. It can be seen from the figure that the carbon nanotube tube has no effect on the softening temperature and the melting point temperature. The melting point temperature of the modified and unmodified carbon nanotubes is between 127 ° C and 130 ° C, so the unmodified carbon nanotubes and the modified carbon nanotubes are shown in the DSC (Differential Scanning Calorimeter). There is not much change, only the crystallization temperature of polyethylene can be slightly increased.
請參閱第9圖，其係為上述各高分子複合材料(實驗組、控制組及對照組)之表面電阻值對碳奈米管含量之曲線圖。一般根據物質之電性可將之分為三類：導體(conductor)、半導體(semiconductor)及絕緣體(insulator)或介電質(dielectric)。想像一個簡單的原子模型，原子是由帶正電的原子核及圍繞其外的電子所組成的。則導體原子最外層的電子所受的束縛力很弱，可以很容易地從一原子遷移到另一原子。大多數的金屬都屬這種類型。絕緣體或介電質原子中的電子，則被侷限只能在軌道上運動；在正常情況下，它們不能自由移動，甚至施加外電場亦然。半導體的電性則在導體和絕緣體之間，它們只有少量的自由移動電荷。若以能帶理論來推測整體複合材料導電機制即可得知，假如所加入的導電填充物，能以極小的距離彼此間隔著，或甚至 互相碰觸，電子就會以躍遷或傳導的方式，將電荷傳遞並消散至表面，而不會累積在薄膜內部。由第9圖中可看出未經改質的CNT/PE複合材料的表面阻抗值在2wt%含量以下呈現相當不好之分散性，在3wt%時之表面阻抗值已達一平衡，此可能因過多的碳奈米管已超過其門檻滲透(threshold percolation)，因此無法再降低其導電性。然而有機無機之間的作用力若有提升，在無機物之分散性上即會有很大的不同，在加入不同改質後可利用表面阻抗的不同就可觀察碳奈米管在此兩個系統中的分散情形。在MA系統中，因為碳奈米管靠些微的氫鍵、極性偶極力與凡得瓦力與PE-g-MA主鍵相互吸引，而在TAIC的系統裡，因共價鍵形成，進而幫助碳奈米管在複合材料內的分散。如圖所示，MA-g-CNT/PE複合材料的阻抗在2wt%時已下降至1000 Ω/cm2，有明顯之降幅，由其比未改質的CNT/PE複合材料還要低，而TAIC系統，是由碳奈米管和聚乙烯之間經共價鍵結的系統，雖然其鍵結力方面會遠比極性吸引力來得大，但因自身聚集，表現在分散性方面效果稍為較弱。 Please refer to FIG. 9 , which is a graph showing the surface resistance values of the above polymer composite materials (experimental group, control group, and control group) versus carbon nanotube content. Generally, it can be classified into three types according to the electrical properties of the substance: a conductor, a semiconductor, an insulator or a dielectric. Imagine a simple atomic model consisting of a positively charged nucleus and electrons surrounding it. Then the electrons at the outermost layer of the conductor atoms are weakly bound and can easily migrate from one atom to another. Most metals are of this type. Electrons in insulators or dielectric atoms are limited to moving only in orbit; under normal conditions, they cannot move freely, even when an external electric field is applied. The electrical properties of a semiconductor are between the conductor and the insulator, and they have only a small amount of freely moving charge. If the band theory is used to predict the overall composite conductive mechanism, it can be known that if the conductive fillers are added, they can be separated from each other by a very small distance, or even touch each other, and the electrons will be transitioned or conducted. The charge is transferred and dissipated to the surface without accumulating inside the film. It can be seen from Fig. 9 that the surface resistance value of the unmodified CNT/PE composite exhibits a rather poor dispersibility below 2 wt%, and the surface resistance value at 3 wt% has reached a balance, which may Since too many carbon nanotubes have exceeded their threshold percolation, their conductivity cannot be reduced. However, if the interaction between organic and inorganic is improved, there will be a big difference in the dispersibility of the inorganic substances. After adding different modifications, the surface impedance can be used to observe the carbon nanotubes in the two systems. The dispersion in the situation. In the MA system, because the carbon nanotubes rely on a slight hydrogen bond, the polar dipole force and the van der Waals force and the PE-g-MA primary bond attract each other, in the TAIC system, the covalent bond is formed, thereby helping the carbon. The dispersion of the nanotubes within the composite. As shown, the impedance of the MA-g-CNT/PE composite has dropped to 1000 Ω/cm 2 at 2 wt%, with a significant decrease, which is lower than that of the unmodified CNT/PE composite. The TAIC system is a system of covalent bonding between carbon nanotubes and polyethylene. Although its bonding force is much larger than the polarity attraction, it is slightly more effective in dispersibility due to its own aggregation. Weak.
因此，由上述實施例之實驗結果，可得知本發明經改質之碳奈米管在聚乙烯中有較好的分散性，可兼顧達成用較低的用量且提升高分子複合材料之電氣性質之功效。 Therefore, from the experimental results of the above examples, it can be known that the modified carbon nanotube of the present invention has good dispersibility in polyethylene, and can achieve the electrical use of a lower amount and improve the polymer composite material. The effect of nature.
以上所述僅為舉例性，而非為限制性者。任何未脫離本發明之精神與範疇，而對其進行之等效修改或變更，均應包含於後附之申請專利範圍中。 The above is intended to be illustrative only and not limiting. Any equivalent modifications or alterations to the spirit and scope of the invention are intended to be included in the scope of the appended claims.
S11-S13‧‧‧流程步驟 S11-S13‧‧‧ Process steps
第1圖係為本發明之高分子複合材料之製造方法之步驟流程圖；第2圖係為本發明之高分子複合材料之一實施例之化學結構圖；第3圖係為各高分子複合材料(實驗組、控制組及對照組)之熱變形溫度對碳奈米管含量之曲線圖；第4圖係為各高分子複合材料(實驗組、控制組及對照組)之拉伸強度對碳奈米管含量之曲線圖；第5圖係為各高分子複合材料(實驗組、控制組及對照組)之缺口耐衝擊強度對碳奈米管含量之曲線圖；第6圖係為各高分子複合材料(實驗組、控制組及對照組)之TGA微分曲線圖；第7圖係為各高分子複合材料(實驗組、控制組及對照組)之TGA最大熱裂解圖；第8圖係為各高分子複合材料(實驗組、控制組及對照組)之DSC曲線圖；以及第9圖係為各高分子複合材料(實驗組、控制組及對照組)之表面電阻值對碳奈米管含量之曲線圖。 1 is a flow chart showing the steps of a method for producing a polymer composite material of the present invention; FIG. 2 is a chemical structure diagram of an embodiment of the polymer composite material of the present invention; and FIG. 3 is a composite of various polymers. The curves of the heat distortion temperature of the materials (experimental group, control group and control group) on the content of carbon nanotubes; the fourth figure shows the tensile strength of each polymer composite (experimental group, control group and control group) The graph of the carbon nanotube content; the fifth graph is the graph of the notched impact strength of the polymer composites (experimental group, control group and control group) on the carbon nanotube content; TGA differential curve of polymer composites (experimental group, control group and control group); Figure 7 is the TGA maximum thermal cracking diagram of each polymer composite material (experimental group, control group and control group); Figure 8 The DSC curve of each polymer composite material (experimental group, control group and control group); and the 9th figure is the surface resistance value of each polymer composite material (experimental group, control group and control group) to carbon A graph of rice tube content.
S11-S13‧‧‧流程步驟 S11-S13‧‧‧ Process steps
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