TWI399406B - Preparation of polybenzoxazine / carbon nanotubes composite - Google Patents

Description

聚苯并噁嗪(polybenzoxazine)/奈米碳管複合材料之製備方法Method for preparing polybenzoxazine/nanocarbon tube composite material

本發明係有關於一種複合材料之製備方法，尤指一種聚苯并噁嗪(polybenzoxazine)/奈米碳管複合材料之製備方法。The invention relates to a preparation method of a composite material, in particular to a preparation method of a polybenzoxazine/nanocarbon tube composite material.

人類歷史與材料的發展有著密不可分的關係，二十世紀中期以來，金屬材料、陶瓷材料及高分子材料為社會文明的主要材料。隨著社會文明的發展，目前社會所需要的材料也越來越多元化，金屬材料、陶瓷材料及高分子材料這三種基本材料的物化與機械性質已不敷多元化應用所需。隨後即產生複合材料，複合材料是由兩種以上的基本材料結合而成，不僅保有個別材料的性質特徵，複合材料之整體性能，如：堅韌特性、機械強度，往往超越單一材料。由於不同材料界面作用力隨著分散相的粒徑之減小而增加，於西元1982年至西元1983年之間，產生奈米材料，奈米材料即表示材料的分散粒徑在奈米範圍。在奈米級混成所得的複合材料具有許多獨特的高功能性質，在電子、磁性、光學元件及結構材料的開發與應用上，都有極大的潛力。西元1990年起，奈米複合材料的研究蓬勃發展，並在諸多應用領域已有數種商品化的實例，顯見奈米複合材料是未來的趨勢。Human history and material development are inextricably linked. Since the middle of the 20th century, metal materials, ceramic materials and polymer materials have been the main materials of social civilization. With the development of social civilization, the materials needed by the society are becoming more and more diversified. The materialization and mechanical properties of the three basic materials of metal materials, ceramic materials and polymer materials are insufficient for diversified applications. The composite material is then produced. The composite material is composed of two or more basic materials. Not only the properties of the individual materials are preserved, but the overall properties of the composite materials, such as toughness and mechanical strength, often exceed a single material. Since the interfacial force of different materials increases with the decrease of the particle size of the dispersed phase, between 1982 and 1983, a nanomaterial is produced, and the nanomaterial indicates that the dispersed particle diameter of the material is in the nanometer range. The composites obtained in the nano-scale hybrid have many unique high-functional properties, and have great potential in the development and application of electronic, magnetic, optical components and structural materials. Since 1990, research on nanocomposites has flourished, and there have been several commercial examples in many fields of application. It is obvious that nanocomposites are the future trend.

目前電子產業之趨勢為結合電子產品與高分子材料，因此，高性能高分子材料之開發為目前重要的課題。一般高分子材料具有強度不足、尺寸安定性不佳及耐熱性差之問題，導致無法應用於電子產品。相較於無機材料、陶瓷材料及鋼鐵材料，高分子材料之耐熱性較差為其應用上最大的限制，所以目前必須開發熱穩定性高分子材料。At present, the trend of the electronics industry is to combine electronic products with polymer materials. Therefore, the development of high-performance polymer materials is an important issue at present. Generally, polymer materials have problems of insufficient strength, poor dimensional stability, and poor heat resistance, and thus cannot be applied to electronic products. Compared with inorganic materials, ceramic materials and steel materials, the heat resistance of polymer materials is the biggest limitation of its application, so it is necessary to develop thermal stability polymer materials.

目前使用的積體電路基材及半導體封裝材料，大都以熱固樹脂為主，熱固性樹脂大量使用於一般的複合材料，一般使用的熱固性樹脂包括不飽和樹脂、酚醛樹脂、環氧樹脂、夫喃樹脂、有機矽樹脂等。其中酚醛樹脂是最早商業化的樹脂之一，其主要由酚與甲醛縮合而成。由於酚醛樹脂原料取得容易，並具有合成方便、良好的機械強度、熱安定性、電絕緣性、尺寸安定性、耐化學藥品性等特點，目前已廣泛地應用於電器、絕熱材料與 複合材料。再者，以酚醛樹脂為基材之複合材料因具有防火、難燃等特性，已成為重要的防火材料用樹脂，但是製造酚醛樹脂所使用之酚有致癌的疑慮，而且其受熱時所釋放揮發性氣體對人體健康及環境衛生有不利的影響。Most of the integrated circuit substrates and semiconductor packaging materials currently used are mainly thermosetting resins. Thermosetting resins are widely used in general composite materials. The commonly used thermosetting resins include unsaturated resins, phenolic resins, epoxy resins, and fusphon. Resin, organic resin, etc. Among them, phenolic resin is one of the earliest commercial resins, which is mainly formed by condensation of phenol and formaldehyde. Because phenolic resin raw materials are easy to obtain, and have the characteristics of convenient synthesis, good mechanical strength, thermal stability, electrical insulation, dimensional stability, chemical resistance, etc., they have been widely used in electrical appliances and thermal insulation materials. Composite material. Furthermore, the composite material based on phenolic resin has become an important resin for fireproof materials because of its properties of fireproofing and flame retardancy. However, the phenol used in the manufacture of phenolic resin has carcinogenic concerns and is volatilized when heated. Sexual gases have an adverse effect on human health and environmental hygiene.

另一類最常使用的熱固性樹脂為環氧樹脂，其具有很高的拉伸強度和模數、優良的尺寸安定性、熱安定性與抗化學藥品性、由於環氧樹脂具有上述多項性能，因此有多種用途，除了一般黏著外可應用領域包括結構材料、航空載具和飛機上纖維補強複合材料，近年來廣泛地應用於光電產業中，從印刷電路板、積體電路封裝，到LED灌注、LCD乃至於OLED封裝等皆屬環氧樹脂應用的領域。但是環氧樹脂在應用上最大的缺點在於其性質太脆，由於高密度交聯網狀結構使得產品性質變脆而限制了更進一步的用途，因此增韌環氧樹脂亦是現今相當熱門的研究。Another type of thermosetting resin that is most commonly used is epoxy resin, which has high tensile strength and modulus, excellent dimensional stability, thermal stability and chemical resistance, and because of the above-mentioned properties of epoxy resin, There are many uses, in addition to general adhesive applications, including structural materials, aviation vehicles and aircraft fiber-reinforced composite materials, which have been widely used in the optoelectronic industry in recent years, from printed circuit boards, integrated circuit packages, to LED infusion, LCDs and even OLED packages are in the field of epoxy resin applications. However, the biggest disadvantage of epoxy resin in application is that its properties are too brittle. Due to the high-density cross-network structure, the product properties become brittle and limit further applications. Therefore, toughened epoxy resin is also a very popular research.

而本發明之奈米複合材料使用聚苯并噁嗪(polybenzoxazine)，Polybenzoxazine屬於熱固性樹脂，其擁有很高的玻璃轉移溫度、高模數、低吸水性、好的介電特質等特性。由於其製品的尺寸安定性佳可以製造精密之零件，再者由於其黏度較低可有較高的設計自由度。再加上Polybenzoxazine於合成時不需使用高危險性之原料，於硬化聚合過程不需額外添加酸類或硬化劑，聚合過程不會產生揮發性氣體。此材料之性能優於傳統酚醛樹脂及環氧樹脂預期可應用於高性能複合材料及航太材料。The nanocomposite of the present invention uses polybenzoxazine, which is a thermosetting resin which has high characteristics such as glass transition temperature, high modulus, low water absorption, and good dielectric properties. Due to the dimensional stability of the products, precision parts can be manufactured, and the lower the viscosity, the higher the degree of design freedom. In addition, Polybenzoxazine does not require the use of high-risk materials during the synthesis. No additional acid or hardener is added during the hardening polymerization process, and no volatile gas is generated during the polymerization. The performance of this material is superior to traditional phenolic resins and epoxy resins and is expected to be applied to high performance composite materials and aerospace materials.

本發明之目的之一，係在於提供一種聚苯并噁嗪(polybenzoxazine)/奈米碳管複合材料之製備方法，其利用氧代氮代苯并環己烷(benzoxazine)單體與奈米碳管製備，奈米碳管加入氧代氮代苯并環己烷(benzoxazine)單體會加速氧代氮代苯并環己烷(benzoxazine)單體之開環硬化，以提高聚苯并噁嗪(polybenzoxazine)的玻璃轉移溫度、硬度、尺寸安定性及交聯密度。One of the objects of the present invention is to provide a method for preparing a polybenzoxazine/nanocarbon nanotube composite material which utilizes oxobenzoxazine monomer and nanocarbon. Tube preparation, the addition of oxocarbobenzoate monomer to the carbon nanotube accelerates the ring-opening hardening of the benzoxazine monomer to increase the polybenzoxazine (Polybenzoxazine) glass transition temperature, hardness, dimensional stability and crosslink density.

本發明之目的之一，係在於提供一種聚苯并噁嗪(polybenzoxazine)/奈米碳管複合材料之製備方法，奈米碳管加入氧代氮代苯并環己烷(benzoxazine)單體，可提高的聚苯并噁嗪(polybenzoxazine)/奈米碳管複 合材料之熱穩定性。One of the objects of the present invention is to provide a method for preparing a polybenzoxazine/nanocarbon tube composite, wherein a carbon nanotube is added with a benzoxazine monomer. Increased polybenzoxazine/nanocarbon tube complex The thermal stability of the composite material.

為了達到上述之目的，本發明提供一種聚苯并噁嗪(polybenzoxazine)/奈米碳管複合材料之製備方法，該製備方法係先製備一氧代氮代苯并環己烷(benzoxazine)單體，接著改質一奈米碳管，然後均勻分散該奈米碳管於該氧代氮代苯并環己烷(benzoxazine)單體，得到一奈米混合材料，最後加熱並硬化該奈米混合材料，開環聚合成一聚苯并噁嗪(polybenzoxazine)/奈米碳管複合材料。In order to achieve the above object, the present invention provides a method for preparing a polybenzoxazine/nanocarbon tube composite, which is prepared by first preparing a benzoxazine monomer. And then modifying a carbon nanotube, and then uniformly dispersing the carbon nanotube in the benzoxazine monomer to obtain a nano-mixed material, and finally heating and hardening the nano-mix The material is ring-opened to form a polybenzoxazine/nanocarbon tube composite.

茲為使 貴審查委員對本發明之結構特徵及所達成之功效有更進一步之瞭解與認識，謹佐以較佳之實施例及配合詳細之說明，說明如後：In order to provide a better understanding and understanding of the structural features and efficacies of the present invention, the preferred embodiments and detailed descriptions are provided as follows:

請參閱第一圖，係本發明之一較佳實施例之流程示意圖。如圖所示，本實施例提供一種聚苯并噁嗪(polybenzoxazine)/奈米碳管複合材料之製備方法，其係先執行步驟S10，製備一Benzoxazine單體，接著執行步驟S12，改質一奈米碳管。然後執行步驟S14，均勻分散經改質之該奈米碳管於該Benzoxazine單體，得到一奈米混合材料。最後執行步驟S16，加熱並硬化該奈米混合材料，開環聚合成一Polybenzoxazine/奈米碳管複合材料。Please refer to the first figure, which is a schematic flow chart of a preferred embodiment of the present invention. As shown in the figure, the present embodiment provides a method for preparing a polybenzoxazine/nanocarbon tube composite, which first performs step S10 to prepare a Benzoxazine monomer, and then performs step S12 to modify one. Carbon nanotubes. Then, step S14 is performed to uniformly disperse the modified carbon nanotubes in the Benzoxazine monomer to obtain a nano-mixed material. Finally, step S16 is performed to heat and harden the nano-mixed material and open-loop polymerization into a Polybenzoxazine/nanocarbon tube composite.

[實施例一]製備Benzoxazine單體[Example 1] Preparation of Benzoxazine monomer

請參閱第二圖，本實施例為上述步驟S10之一實施例，該Benzoxazine單體之合成係於500毫升的一三頸反應瓶中。該三頸反應瓶裝上一熱電偶、一冷凝管及一滴液漏斗。製備該Benzoxazine單體係取一甲胺、一酚類及一甲醛製備。製備該Benzoxazine單體係執行步驟S101，取28.5克之雙酚溶於50毫升之甲苯加入該三頸反應瓶，得到一第一混合溶液。接著執行步驟S102，將承載該第一混合溶液之該三頸反應瓶置於一冰浴，並通入一氮氣至承載該第一混合溶液之該三頸反應瓶，且利用一磁石攪拌該第一混合溶液。Referring to the second figure, this embodiment is an example of the above step S10, and the synthesis of the Benzoxazine monomer is in a 500 ml one-neck reaction bottle. The three-neck reaction bottle is equipped with a thermocouple, a condenser and a dropping funnel. The Benzoxazine single system was prepared by taking monomethylamine, monophenols and monoformaldehyde. The Benzoxazine single system was prepared to carry out step S101, and 28.5 g of bisphenol was dissolved in 50 ml of toluene to be added to the three-necked reaction flask to obtain a first mixed solution. Next, in step S102, the three-neck reaction bottle carrying the first mixed solution is placed in an ice bath, and a nitrogen gas is introduced into the three-neck reaction bottle carrying the first mixed solution, and the magnet is stirred by a magnet. A mixed solution.

然後執行步驟S103，另取過量的甲醛溶於80毫升，得到該第二混合 溶液，再執行步驟S104，該第二混合溶液置於該滴液漏斗慢慢滴入承載該第一混合溶液之該三頸反應瓶，待該第二混合溶液完全滴入承載該第一混合溶液之該三頸反應瓶後，攪拌該第一混合溶液及該第二混合溶液，得到一第三混合溶液。接著執行步驟S105，另取14.25克之甲胺加入20毫升之甲苯，得到一第四混合溶液。然後執行步驟S106，該第四混合溶液慢慢滴入承載該第三混合溶液之該三頸反應瓶，待該第四混合溶液完全滴入承載該第三混合溶液之該三頸反應瓶後，攪拌該第三混合溶液及該第四混合溶液，得到一第五混合溶液。Then, step S103 is performed, and another excess formaldehyde is dissolved in 80 ml to obtain the second mixture. The solution is further step S104, the second mixed solution is placed in the dropping funnel and slowly dropped into the three-neck reaction bottle carrying the first mixed solution, and the second mixed solution is completely dropped into the first mixed solution. After the three-neck reaction flask, the first mixed solution and the second mixed solution are stirred to obtain a third mixed solution. Then, step S105 is performed, and another 14.25 g of methylamine is added to 20 ml of toluene to obtain a fourth mixed solution. Then, in step S106, the fourth mixed solution is slowly dropped into the three-neck reaction bottle carrying the third mixed solution, and after the fourth mixed solution is completely dropped into the three-neck reaction bottle carrying the third mixed solution, The third mixed solution and the fourth mixed solution are stirred to obtain a fifth mixed solution.

接著執行步驟S107，承載該第五混合溶液之該三頸反應瓶移到一油浴中，繼續攪拌並加熱該第五混合溶液，先慢速升溫一小時至攝氏60度，再過一小時升溫至攝氏110度，然後回流8小時，該第五混合溶液產生一黏性液體。然後執行步驟S108，真空抽除該第五混合溶液之一溶劑，剩下該黏性液體，該黏性液體溶於200毫升之一***溶液，得到一第六混合溶液。接著執行步驟S109，使用2N的氫氧化鈉溶液及去離子水多次清洗該第六混合溶液，將該第六混合溶液中未反應之甲醛和甲胺去除，得到一第七混合溶液。然後執行步驟S110，加入無水硫酸鎂去除該第七混合溶液之水分，得到一化合物，最後執行步驟S111，減壓蒸發該化合物所含之***，進而得到該Benzoxazine單體。Then, in step S107, the three-neck reaction bottle carrying the fifth mixed solution is moved to an oil bath, and the fifth mixed solution is further stirred and heated, and the temperature is slowly increased by one hour to 60 degrees Celsius, and then heated for one hour. At a temperature of 110 degrees Celsius and then refluxed for 8 hours, the fifth mixed solution produced a viscous liquid. Then, in step S108, one solvent of the fifth mixed solution is vacuum-extracted, and the viscous liquid is left. The viscous liquid is dissolved in 200 ml of one of diethyl ether solution to obtain a sixth mixed solution. Next, in step S109, the sixth mixed solution is washed a plurality of times using a 2N sodium hydroxide solution and deionized water, and the unreacted formaldehyde and methylamine in the sixth mixed solution are removed to obtain a seventh mixed solution. Then, step S110 is performed, anhydrous magnesium sulfate is added to remove the water of the seventh mixed solution to obtain a compound, and finally, step S111 is performed, and the ether contained in the compound is evaporated under reduced pressure to obtain the Benzoxazine monomer.

[實施例二]改質奈米碳管[Example 2] Modified carbon nanotube

本實施例為上述步驟S12之一實施例，改質該奈米碳管係先純化該奈米碳管，再酸化經純化之該奈米碳管。其中純化該奈米碳管係使用化學氧化法、熱氧化法、超音波輔助過濾法、層析法或微波加熱法進行純化。本實施例係選用微波反應純化法純化該奈米碳管，請參閱第三圖，純化該奈米碳管係先執行步驟S121，將0.5克奈米碳管置入250毫升的反應瓶，並加入100毫升3M的硝酸溶液，且利用超音波震盪半小時，使奈米碳管均勻分散於硝酸溶液中，得到一第一混合溶液。本實施例使用一強氧化劑使該奈米碳管之表面官能基化，本實施例使用硝酸溶液為該強氧化劑，該強氧 化劑亦可使用硫酸或其他組合，如此可使該奈米碳管之表面官能基化係使接上羧基、羰基或羥基。This embodiment is an embodiment of the above step S12. The carbon nanotube is modified to first purify the carbon nanotube, and then the purified carbon nanotube is acidified. The purified carbon nanotubes are purified by chemical oxidation, thermal oxidation, ultrasonic assisted filtration, chromatography or microwave heating. In this embodiment, the carbon nanotubes are purified by microwave reaction purification method. Referring to the third figure, the carbon nanotubes are purified. First, step S121 is performed, and 0.5 g of carbon nanotubes are placed in a 250 ml reaction bottle. 100 ml of a 3 M nitric acid solution was added, and ultrasonic waves were shaken for half an hour to uniformly disperse the carbon nanotubes in the nitric acid solution to obtain a first mixed solution. In this embodiment, a surface of the carbon nanotube is functionalized by using a strong oxidizing agent. In this embodiment, a nitric acid solution is used as the strong oxidizing agent, and the strong oxygen is used. Sulfuric acid or other combinations may also be used, such that the surface of the carbon nanotubes is functionalized to attach a carboxyl group, a carbonyl group or a hydroxyl group.

接著執行步驟S122，將該反應瓶置入一微波反應器，該微波反應器之溫度設定為攝氏120度，設定一加熱時間及一固定功率，然後以磁石攪拌該第一混合溶液，其中該加熱時間係介於10分鐘與40分鐘之間，該加熱時間越久越佳，該固定功率係介於300瓦與500瓦之間，該固定功率越高，將會破壞該奈米碳管的型態。Then, in step S122, the reaction bottle is placed in a microwave reactor, the temperature of the microwave reactor is set to 120 degrees Celsius, a heating time and a fixed power are set, and then the first mixed solution is stirred by a magnet, wherein the heating is performed. The time system is between 10 minutes and 40 minutes. The longer the heating time is, the fixed power is between 300 watts and 500 watts. The higher the fixed power, the type of the carbon nanotubes will be destroyed. .

然後執行步驟S123，靜置承載該第一混合溶液之該反應瓶至室溫，利用一高速離心機分離該第一混合溶液，分離出該奈米碳管及該硝酸溶液。接著執行步驟S124，以去離子水潤洗該奈米碳管多次至溶液PH值幾近中性。最後執行步驟S125，該奈米碳管置於一水溶液中，並超音波震盪一小時，然後以烘箱除去該水溶液，得到經微波純化之該奈米碳管。Then, in step S123, the reaction flask carrying the first mixed solution is allowed to stand at room temperature, and the first mixed solution is separated by a high-speed centrifuge to separate the carbon nanotube and the nitric acid solution. Then, step S124 is performed to rinse the carbon nanotubes with deionized water several times until the pH of the solution is nearly neutral. Finally, in step S125, the carbon nanotube is placed in an aqueous solution and ultrasonically shaken for one hour, and then the aqueous solution is removed in an oven to obtain the microwave-purified carbon nanotube.

接著將經微波純化之該奈米碳管進行酸化，請參閱第四圖，酸化經純化之該奈米碳管係先執行步驟S126，取0.5克之經純化之該奈米碳管加入40毫升的一混合溶液，該混合溶液為硫酸與硝酸混合，硫酸與硝酸之組成比為3：1，接著執行步驟S127，已加入該奈米碳管之該混合溶液於攝氏50度下利用磁石攪拌24小時。然後執行步驟S128，抽氣過濾已加入該奈米碳管之該混合溶液，得到一經酸化之該奈米碳管，接著執行步驟S129，利用去離子水與甲醇反覆沖洗經酸化之該奈米碳管四次，最後執行步驟S130，經酸化之該奈米碳管置於烘箱進行烘乾，該烘箱的溫度設定為攝氏60度，其烘乾時間為24小時。The microwave purified carbon nanotubes are then acidified. Please refer to the fourth figure. The acidified purified carbon nanotubes are first subjected to step S126, and 0.5 g of the purified carbon nanotubes are added to 40 ml. a mixed solution, the mixed solution is sulfuric acid mixed with nitric acid, the composition ratio of sulfuric acid to nitric acid is 3:1, and then step S127 is performed, and the mixed solution which has been added to the carbon nanotube is stirred by magnet for 24 hours at 50 degrees Celsius. . Then, in step S128, the mixed solution which has been added to the carbon nanotubes is suction-filtered to obtain an acidified carbon nanotube, and then step S129 is performed, and the acidified nanocarbon is repeatedly washed with deionized water and methanol. After four times, the final step S130 is performed, and the acidified carbon nanotube is placed in an oven for drying. The temperature of the oven is set to 60 degrees Celsius, and the drying time is 24 hours.

[實施例三]製備奈米混合材料[Example 3] Preparation of nano-mixed materials

本實施例之該奈米混合材料係利用溶液掺合法製備，請參閱第五圖，製備該奈米混合材料係先執行步驟S141，取經改質之該奈米碳管使用超音波震盪30分鐘，將該奈米碳管平均分散於4毫升之THF，得到一第一混合溶液。接著執行步驟S143，取2克之該Benzoxazine單體溶於6毫升之THF，得到一第二混合溶液。其中該Benzoxazine單體與該奈米碳管之組成比例 不超過1.5phr。再執行步驟S145，混合該第一混合溶液及該第二混合溶液，得到一第三混合溶液，該第三混合溶液於室溫下超音波震盪30分鐘，再利用磁石攪拌該第三混合溶液，攪拌時間為2小時。接著執行步驟S147，將該第三混合溶液倒入一鋁盤，並以磁石攪拌該第三混合溶液，且升溫去除該第三混合溶液之部分溶劑。最後執行步驟S149，待該第三混合溶液呈一膠狀物後，送入烘箱去除該膠狀物之溶劑，烘箱溫度為攝氏60度，去除該膠狀物之溶劑後，得到該奈米混合材料。The nano-mixed material of the present embodiment is prepared by solution doping. Please refer to the fifth figure. The preparation of the nano-mixed material is first performed in step S141, and the modified carbon nanotube is oscillated using ultrasonic waves for 30 minutes. The carbon nanotubes were evenly dispersed in 4 ml of THF to obtain a first mixed solution. Next, in step S143, 2 g of the Benzoxazine monomer is dissolved in 6 ml of THF to obtain a second mixed solution. Wherein the composition ratio of the Benzoxazine monomer to the carbon nanotube No more than 1.5 phr. Then, the step S145 is performed, the first mixed solution and the second mixed solution are mixed to obtain a third mixed solution, which is ultrasonically shaken at room temperature for 30 minutes, and then the third mixed solution is stirred by the magnet. The stirring time was 2 hours. Next, in step S147, the third mixed solution is poured into an aluminum pan, and the third mixed solution is stirred with a magnet, and a part of the solvent of the third mixed solution is removed by heating. Finally, in step S149, after the third mixed solution is in the form of a gel, it is sent to an oven to remove the solvent of the gel. The oven temperature is 60 degrees Celsius, and the solvent of the gel is removed to obtain the nanomix. material.

將利用上述方法所製備之該Polybenzoxazine/奈米碳管複合材料進行各種檢驗，由該Polybenzoxazine/奈米碳管複合材料之傅立葉轉換紅外光光譜可知，該Benzoxazine單體已經成功硬化成Polybenzoxazine，而該奈米碳管的加入可催化該Benzoxazine單體之硬化速度。然而由該Polybenzoxazine/奈米碳管複合材料之掃描式電子顯微圖、拉曼光譜及熱重分析圖可知，經改質之該奈米碳管確實可以去除該奈米碳管之金屬觸媒及不定型碳。從該Polybenzoxazine/奈米碳管複合材料利用微差掃描熱卡計檢驗之結果可知，該奈米碳管的加入可催化Polybenzoxazine之硬化過程，如：可降低該Benzoxazine單體所需的硬化熱、最大固化溫度及起始溫度，並可提升該Benzoxazine單體之玻璃轉移溫度。由該Polybenzoxazine/奈米碳管複合材料之熱重分析圖可知，加入該奈米碳管可提升Polybenzoxazine的殘餘灰份。由該Polybenzoxazine/奈米碳管複合材料之熱重分析圖可知，加入該奈米碳管可提升Polybenzoxazine的殘餘灰份。由該Polybenzoxazine/奈米碳管複合材料之動態機械分析圖可知，加入該奈米碳管可提升Polybenzoxazine的玻璃轉移溫度及儲存模數，並增加Polybenzoxazine的交聯密度，且降低Polybenzoxazine的損耗模數。由該Polybenzoxazine/奈米碳管複合材料之熱機械分析圖可知，加入該奈米碳管會降低Polybenzoxazine之熱膨脹係數。The Polybenzoxazine/nanocarbon tube composite prepared by the above method was subjected to various tests, and the Benzoxazine monomer was successfully hardened into Polybenzoxazine by the Fourier transform infrared spectrum of the Polybenzoxazine/nanocarbon tube composite. The addition of a carbon nanotube catalyzes the rate of hardening of the Benzoxazine monomer. However, from the scanning electron micrograph, Raman spectroscopy and thermogravimetric analysis of the Polybenzoxazine/nanocarbon nanotube composite, it can be seen that the modified carbon nanotube can indeed remove the metal catalyst of the carbon nanotube. And amorphous carbon. From the results of the differential scanning calorimeter test of the Polybenzoxazine/nanocarbon tube composite material, the addition of the carbon nanotube can catalyze the hardening process of the Polybenzoxazine, for example, the heat of hardening required for the Benzoxazine monomer, The maximum curing temperature and starting temperature, and can increase the glass transition temperature of the Benzoxazine monomer. From the thermogravimetric analysis of the Polybenzoxazine/nanocarbon nanotube composite, it can be seen that the addition of the carbon nanotube can increase the residual ash of the Polybenzoxazine. From the thermogravimetric analysis of the Polybenzoxazine/nanocarbon nanotube composite, it can be seen that the addition of the carbon nanotube can increase the residual ash of the Polybenzoxazine. From the dynamic mechanical analysis of the Polybenzoxazine/nanocarbon nanotube composite, the addition of the carbon nanotubes can increase the glass transition temperature and storage modulus of Polybenzoxazine, increase the crosslinking density of Polybenzoxazine, and reduce the loss modulus of Polybenzoxazine. . From the thermomechanical analysis of the Polybenzoxazine/nanocarbon nanotube composite, it is known that the addition of the carbon nanotube reduces the thermal expansion coefficient of the Polybenzoxazine.

由上述可知，本發明提供一種Polybenzoxazine/奈米碳管複合材料之製備方法，其利用Benzoxazine單體與奈米碳管製備，奈米碳管加入Benzoxazine單體會加速Benzoxazine單體之開環硬化，其所製備之該 Polybenzoxazine/奈米碳管複合材料具有高玻璃轉移溫度、高硬度、高尺寸安定性及高交聯密度，更具有較佳的熱穩定性。It can be seen from the above that the present invention provides a method for preparing a Polybenzoxazine/nanocarbon tube composite material, which is prepared by using a Benzoxazine monomer and a carbon nanotube, and the addition of a Benzoxazine monomer to a carbon nanotube accelerates the ring-opening hardening of the Benzoxazine monomer. The preparation thereof Polybenzoxazine/nanocarbon nanotube composites have high glass transition temperature, high hardness, high dimensional stability and high crosslink density, and have better thermal stability.

綜上所述，本發明係實為一具有新穎性、進步性及可供產業利用者，應符合我國專利法所規定之專利申請要件無疑，爰依法提出發明專利申請，祈 鈞局早日賜准利，至感為禱。In summary, the present invention is a novelty, progressive and available for industrial use, and should conform to the patent application requirements stipulated in the Patent Law of China, and the invention patent application is filed according to law. Lee, the feeling is a prayer.

惟以上所述者，僅為本發明之一較佳實施例而已，並非用來限定本發明實施之範圍，舉凡依本發明申請專利範圍所述之形狀、構造、特徵及精神所為之均等變化與修飾，均應包括於本發明之申請專利範圍內。However, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and the shapes, structures, features, and spirits described in the claims are equivalently changed. Modifications are intended to be included in the scope of the patent application of the present invention.

第一圖係本發明之一較佳實施例之流程示意圖；第二圖係本發明之另一較佳實施例之製備Benzoxazine單體之流程示意圖；第三圖係本發明之另一較佳實施例之微波純化奈米碳管之流程示意圖；第四圖係本發明之另一較佳實施例之酸化奈米碳管之流程示意圖；以及第五圖係本發明之另一較佳實施例之製備奈米混合材料之流程示意圖。The first drawing is a schematic flow chart of a preferred embodiment of the present invention; the second drawing is a schematic flow chart of preparing a Benzoxazine monomer according to another preferred embodiment of the present invention; and the third drawing is another preferred embodiment of the present invention. Schematic diagram of a flow of a microwave-purified carbon nanotube; a fourth diagram is a schematic flow diagram of an acidified carbon nanotube according to another preferred embodiment of the present invention; and a fifth diagram is another preferred embodiment of the present invention. A schematic diagram of the process for preparing a nano-mixed material.

Claims (13)

一種聚苯并噁嗪(polybenzoxazine)/奈米碳管複合材料之製備方法，係包含：製備一氧代氮代苯并環己烷(benzoxazine)單體；改質一奈米碳管；均勻分散經改質之該奈米碳管於該氧代氮代苯并環己烷(benzoxazine)單體，得到一奈米混合材料；以及加熱並硬化該奈米混合材料，開環聚合成一聚苯并噁嗪(polybenzoxazine)/奈米碳管複合材料。 A method for preparing a polybenzoxazine/nanocarbon tube composite comprises: preparing a benzoxazine monomer; modifying a carbon nanotube; uniformly dispersing The modified carbon nanotube is used in the oxyx benzoxazine monomer to obtain a nanometer mixed material; and the nano hybrid material is heated and hardened, and the ring-opening polymerization is carried out into a polyphenylene Polybenzoxazine/nanocarbon tube composite. 如申請專利範圍第1項所述之製備方法，其中製備該Benzoxazine單體係取一甲胺、一酚類及一甲醛製備該氧代氮代苯并環己烷(benzoxazine)單體。 The preparation method according to claim 1, wherein the Benzoxazine single system is prepared by taking monomethylamine, monophenol and monoformaldehyde to prepare the oxobenzobenzoate monomer. 如申請專利範圍第2項所述之製備方法，其中製備該氧代氮代苯并環己烷(benzoxazine)單體係包含：將該酚類溶於一甲苯溶液，得到一第一混合溶液；將該第一混合溶液置於一冰浴，通入一氮氣至該第一混合溶液，並攪拌該第一混合溶液；將該甲醛溶於一甲苯溶液，得到一第二混合溶液；將該第二混合溶液滴入該第一混合溶液，並攪拌該第一混合溶液及該第二混合溶液得到一第三混合溶液；將該甲胺溶於一甲苯溶液，得到一第四混合溶液；將該第四混合溶液滴入該第三混合溶液，並攪拌該第三混合溶液及該第四混合溶液得到一第五混合溶液；將該第五混合溶液置於一油浴，攪拌並加熱該第五混合溶液，得到一黏性液體；將該黏性液體溶於一***溶液，得到一第六混合溶液； 清洗該第六混合溶液，去除該第六混合溶液之該甲醛及該甲胺，得到一第七混合溶液；去除該第七混合溶液之水分，得到一化合物；以及去除該化合物所含之該***，得到該氧代氮代苯并環己烷(benzoxazine)單體。 The preparation method of claim 2, wherein the preparation of the oxyxazine benzoxazine single system comprises: dissolving the phenol in a toluene solution to obtain a first mixed solution; Putting the first mixed solution in an ice bath, introducing a nitrogen gas to the first mixed solution, and stirring the first mixed solution; dissolving the formaldehyde in a toluene solution to obtain a second mixed solution; Diluting the mixed solution into the first mixed solution, and stirring the first mixed solution and the second mixed solution to obtain a third mixed solution; dissolving the methylamine in a toluene solution to obtain a fourth mixed solution; The fourth mixed solution is dropped into the third mixed solution, and the third mixed solution and the fourth mixed solution are stirred to obtain a fifth mixed solution; the fifth mixed solution is placed in an oil bath, stirred and heated to the fifth Mixing the solution to obtain a viscous liquid; dissolving the viscous liquid in an ether solution to obtain a sixth mixed solution; Washing the sixth mixed solution, removing the formaldehyde and the methylamine of the sixth mixed solution to obtain a seventh mixed solution; removing the moisture of the seventh mixed solution to obtain a compound; and removing the ether contained in the compound The oxobenzobenzoin monomer was obtained. 如申請專利範圍第1項所述之製備方法，其中改質該奈米碳管之步驟係包含：純化該奈米碳管；以及酸化經純化之該奈米碳管。 The preparation method of claim 1, wherein the step of modifying the carbon nanotube comprises: purifying the carbon nanotube; and acidifying the purified carbon nanotube. 如申請專利範圍第4項所述之製備方法，其中純化該奈米碳管係利用化學氧化法、熱氧化法、超音波輔助過濾法、層析法或微波加熱法。 The preparation method according to the fourth aspect of the invention, wherein the carbon nanotube system is purified by chemical oxidation, thermal oxidation, ultrasonic assisted filtration, chromatography or microwave heating. 如申請專利範圍第1項所述之製備方法，其中改質該奈米碳管之步驟係包含：使用一強氧化劑使該奈米碳管之表面官能基化。 The preparation method of claim 1, wherein the step of modifying the carbon nanotube comprises: functionalizing a surface of the carbon nanotube with a strong oxidizing agent. 如申請專利範圍第6項所述之製備方法，其中該強氧化劑係為硝酸或硫酸或其組合。 The preparation method of claim 6, wherein the strong oxidizing agent is nitric acid or sulfuric acid or a combination thereof. 如申請專利範圍第6項所述之製備方法，其中該奈米碳管之表面官能基化係使接上羧基。 The preparation method of claim 6, wherein the surface functionalization of the carbon nanotube is such that a carboxyl group is attached. 如申請專利範圍第6項所述之製備方法，其中該奈米碳管之表面官能基化係使接上羰基。 The preparation method of claim 6, wherein the surface functionalization of the carbon nanotube is such that a carbonyl group is attached. 如申請專利範圍第6項所述之製備方法，其中該奈米碳管之表面官能基化係使接上羥基。 The preparation method of claim 6, wherein the surface functionalization of the carbon nanotube is such that a hydroxyl group is attached. 如申請專利範圍第1項所述之製備方法，其中均勻分散該奈米碳管於該氧代氮代苯并環己烷(benzoxazine)單體係利用溶液掺合法。 The preparation method according to claim 1, wherein the carbon nanotubes are uniformly dispersed in the oxyx benzoxazine single system by solution doping. 如申請專利範圍第11項所述之製備方法，其中均勻分散該奈米碳管於該氧代氮代苯并環己烷(benzoxazine)單體之步驟係包含：均勻分散該奈米碳管於一THF溶液，得到一第一混合溶液；將該氧代氮代苯并環己烷(benzoxazine)單體溶於一THF溶液，得到一 第二混合溶液；混合該第一混合溶液及該第二混合溶液，得到一第三混合溶液；攪拌並加熱該第三混合溶液，得到一膠狀物；以及烘烤該膠狀物，得到該奈米混合材料。 The preparation method according to claim 11, wherein the step of uniformly dispersing the carbon nanotube in the benzoxazine monomer comprises: uniformly dispersing the carbon nanotube a THF solution to obtain a first mixed solution; the oxobenzobenzoate monomer is dissolved in a THF solution to obtain a a second mixed solution; mixing the first mixed solution and the second mixed solution to obtain a third mixed solution; stirring and heating the third mixed solution to obtain a jelly; and baking the gel to obtain the Nano hybrid material. 如申請專利範圍第12項所述之製備方法，其中該氧代氮代苯并環己烷(benzoxazine)單體及該奈米碳管之組成比例係小於1.5phr。 The preparation method according to claim 12, wherein the benzoxazine monomer and the carbon nanotube have a composition ratio of less than 1.5 phr.