WO2021103850A1 - Preparation method for modified carbon nanotube and use thereof - Google Patents
Preparation method for modified carbon nanotube and use thereof Download PDFInfo
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- WO2021103850A1 WO2021103850A1 PCT/CN2020/121849 CN2020121849W WO2021103850A1 WO 2021103850 A1 WO2021103850 A1 WO 2021103850A1 CN 2020121849 W CN2020121849 W CN 2020121849W WO 2021103850 A1 WO2021103850 A1 WO 2021103850A1
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- carbon nanotubes
- modified carbon
- carbon nanotube
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- ethyl orthosilicate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
Definitions
- the invention belongs to the technical field of thermal conductivity and insulation, and specifically relates to a method for preparing modified carbon nanotubes and applications thereof.
- the power of the motor is continuously increasing, and the power consumption of the motor is also increasing at the same time, which causes the working temperature of the motor to become higher and higher, and the heat dissipation capacity of the motor components, especially the insulating parts, directly affects the temperature of the motor. If the motor temperature rise exceeds the limit, it will cause insulation aging, coil breakdown, and motor burnout. If the insulating varnish has both high thermal conductivity and electrical insulation performance, it can effectively reduce the temperature rise of the motor windings, thereby increasing The output power of the motor, and the insulating paint in the prior art still has the problem that it is difficult to have excellent thermal conductivity, insulation and mechanical properties, which greatly limits the quality and life of the motor.
- CNTs carbon nanotubes
- thermal conductive materials have received extensive attention because of their excellent thermal conductivity, mechanical strength, electrical conductivity and other properties.
- Maxwell’s mixing theory adding 1% of carbon nanotubes can theoretically improve The thermal conductivity of organic compounds is 50 times, so it is expected to solve the negative effects of high doping mentioned above.
- high doping reduces the mechanical properties of insulating varnishes; however, for insulating materials, carbon nanotubes have high
- the high electrical conductivity and incompatibility with the surface and interface of organic matter limit the application of carbon nanotubes as thermally conductive materials in insulating materials.
- the purpose of the present invention is to overcome the shortcomings of the prior art and provide a new method for preparing modified carbon nanotubes.
- the modified carbon nanotubes prepared by the method can combine high thermal conductivity, low electrical conductivity, and compatibility with organics. Good characteristics.
- the invention also provides an application of the modified carbon nanotube prepared by the above method in a thermally conductive insulating material.
- the present invention adopts the following technical solutions:
- a preparation method of modified carbon nanotubes includes the following steps:
- step (2) The surface carboxylated carbon nanotubes prepared in step (1) are dissolved in a mixed solution of water and ethanol, and then ethyl orthosilicate, vinyl triethoxysilane and ammonia are added to react to prepare The modified carbon nanotube is formed, and the surface of the modified carbon nanotube has a vinyl group.
- the modified carbon nanotube produced by the preparation method includes a carbon nanotube core layer and a silica shell layer formed on the surface of the carbon nanotube core layer, the carbon nanotube core layer and Part or all of the silica shell layers are connected by chemical bonds.
- step (2) the reaction is carried out at 30-50°C.
- step (2) the ethyl orthosilicate, the vinyl triethoxy silane and the ammonia are added to the mixed solution in the form of dropwise addition.
- step (2) the step of adding the ethyl orthosilicate, the vinyl triethoxysilane and the ammonia water to the mixed solution is specifically as follows: Part of the mixture of ethyl orthosilicate and the vinyl triethoxy silane is added dropwise to the mixed solution, while a part of the ammonia water is added dropwise to react; then the remaining part of the mixture and the ammonia water are added separately .
- step (2) the feed quality of the surface carboxylated carbon nanotubes, the mixture of the ethyl orthosilicate and the vinyl triethoxysilane, and the ammonia
- the ratio is 1:0.9-1.2:1-1.2.
- step (2) the feed mass ratio of the water to the ethanol is 1:0.95-1.1.
- step (2) the feed mass ratio of one of the ethyl orthosilicate and the vinyl triethoxysilane relative to the other is controlled to be within 3 times.
- the surface carboxylated carbon nanotubes are prepared by mixing and reacting carbon nanotubes with a mixed acid at 105-115°C, and the mixed acid is made of Consists of sulfuric acid and nitric acid.
- the feed mass ratio of the sulfuric acid to the nitric acid is 2-4:1.
- the carbon nanotubes are multi-wall carbon nanotubes and/or single-wall carbon nanotubes.
- the mass fraction of sulfuric acid is 80-98%, and the mass fraction of nitric acid is 60-80%.
- Another technical solution provided by the present invention an application of modified carbon nanotubes produced by the above-mentioned method for preparing modified carbon nanotubes in thermally conductive insulating materials.
- the present invention has the following advantages compared with the prior art:
- the present invention innovatively adopts a specific method to prepare modified carbon nanotubes with vinyl on the surface, and because the prepared modified carbon nanotubes have a chemical bond between the core layer and the shell layer, the modified carbon nanotubes of the present invention It can exist stably and can be applied to insulating varnish with a small amount of addition, and can participate in the cross-linking network of the unsaturated resin of insulating varnish with vinyl bonds, so that the insulating varnish made can not only have excellent thermal conductivity and insulation It can also obtain excellent mechanical properties, overcome the disadvantages of high doping in the prior art that are not conducive to the common impregnation process and the VPI impregnation process, and the temperature resistance level can reach H level.
- the power of the motor is continuously increasing, and the power consumption of the motor is also increasing at the same time, which causes the working temperature of the motor to become higher and higher, and the heat dissipation capacity of the motor components, especially the insulating parts, directly affects the temperature of the motor. If the motor temperature rise exceeds the limit, it will cause insulation aging, coil breakdown, and motor burnout. If the insulating varnish has both high thermal conductivity and electrical insulation performance, it can effectively reduce the temperature rise of the motor windings, thereby increasing The output power of the motor, and the insulating paint in the prior art still has the problem that it is difficult to have excellent thermal conductivity, insulation and mechanical properties, which greatly limits the quality and life of the motor.
- the present invention provides a modified carbon nanotube with a specific structure made by a specific method, which allows the modified carbon nanotube to exist in a core-shell structure, and a silica shell is formed on the surface of the carbon nanotube core layer.
- the two layers are connected by a chemical bond to make the bond tighter and stronger, which is conducive to giving full play to the thermal conductivity of carbon nanotubes and inhibiting the conductivity of carbon nanotubes, and also gives the modified carbon nanotube surface ethylene Base, so that the modified carbon nanotubes can participate in the crosslinking network of organic resins such as unsaturated polyester resins, so that on the one hand, it can ensure that the carbon nanotubes are evenly dispersed in the insulating paint, make full use of their thermal conductivity, and also improve The degree of crosslinking of the resin curing, on the other hand, enables the carbon nanotubes of the present invention to be applied to insulating paint with a small amount of addition, and thus does not affect the mechanical properties and electrical properties of the insulating paint.
- organic resins such as unsaturated polyester resins
- a method for preparing modified carbon nanotubes includes: (1) preparing surface carboxylated carbon nanotubes; (2) preparing the surface carboxylated carbon nanotubes prepared in step (1) The tube is dissolved in a mixed solution of water and ethanol, and then ethyl orthosilicate, vinyl triethoxy silane and ammonia are added to react to form the modified carbon nanotube, the surface of the modified carbon nanotube has Vinyl.
- the modified carbon nanotube produced includes a carbon nanotube core layer and a silica shell layer formed on the surface of the carbon nanotube core layer, the carbon nanotube core layer and the dioxide Part or all of the silicon shell layers are connected by chemical bonds.
- step (2) Add 10 parts of surface carboxylated carbon nanotubes prepared in step (1) to a mixture of 50 parts of water and 50 parts of ethanol, and add 5 parts of ethyl orthosilicate and 5 parts of vinyl triethoxy silane Mix and prepare 10 parts ammonia. Place the carboxylated carbon nanotube solution in an oil bath at 35°C and stir, slowly add 1 part of the mixture of 10 parts of ethyl orthosilicate and vinyl triethoxy silane, and then add dropwise to the above mixture. At the same time, slowly add 1 part of ammonia water, and stir for 30 minutes after the addition is complete; then slowly add the remaining 9 parts of ethyl orthosilicate and vinyl triethoxy silane mixture and 9 parts of ammonia dropwise. After the dripping is completed, the reaction After 2 hours, centrifuged at 10000r/min to obtain modified carbon nanotubes.
- step (2) Add 10 parts of carbon nanotubes with surface carboxylation prepared in step (1) to a mixture of 50 parts of water and 50 parts of ethanol, and add 2.5 parts of ethyl orthosilicate and 7.5 parts of vinyl triethoxy silane Mix and prepare 10 parts ammonia. Place the carboxylated carbon nanotube solution in an oil bath at 40°C and stir, slowly add 1 part of the mixture of 10 parts of ethyl orthosilicate and vinyl triethoxysilane, and then add dropwise to the above mixture. At the same time, slowly add 1 part of ammonia water, and stir for 30 minutes after the addition is complete; then slowly add the remaining 9 parts of ethyl orthosilicate and vinyl triethoxy silane mixture and 9 parts of ammonia dropwise. After the dripping is completed, the reaction After 2 hours, centrifuged at 10000r/min to obtain modified carbon nanotubes.
- step (2) Add 10 parts of surface carboxylated carbon nanotubes prepared in step (1) to a mixture of 50 parts of water and 50 parts of ethanol, and add 7.5 parts of ethyl orthosilicate and 2.5 parts of vinyl triethoxy silane Mix and prepare 10 parts ammonia. Place the carboxylated carbon nanotube solution in an oil bath at 35°C and stir, slowly add 1 part of the mixture of 10 parts of ethyl orthosilicate and vinyl triethoxy silane, and then add dropwise to the above mixture. At the same time, slowly add 1 part of ammonia water, and stir for 30 minutes after the addition is complete; then slowly add the remaining 9 parts of ethyl orthosilicate and vinyl triethoxy silane mixture and 9 parts of ammonia dropwise. After the dripping is completed, the reaction After 2 hours, centrifuged at 10000r/min to obtain modified carbon nanotubes.
- Example 2 It is basically the same as Example 1, except that: "5 parts of ethyl orthosilicate and 5 parts of vinyl triethoxysilane" are replaced with 10 parts of ethyl orthosilicate.
- Example 2 It is basically the same as Example 1, except that: "5 parts of ethyl orthosilicate and 5 parts of vinyl triethoxy silane” are replaced with 10 parts of vinyl triethoxy silane.
- thermally conductive insulating paint In parts by mass, the raw materials of the thermally conductive insulating paint include: 10 parts of isophthalic anhydride, 22 parts of maleic anhydride, and 23.6 parts of 1,2-propylene glycol. Examples 1. Prepare 4 parts of modified carbon nanotubes, 1 part of dibenzoyl peroxide, 0.05 parts of cobalt naphthenate, 23 parts of styrene, and 0.02 parts of hydroquinone.
- the preparation method is as follows: Weigh the raw materials according to the formula, then add isophthalic anhydride, maleic anhydride, 1,2-propanediol, and modified carbon nanotubes into the reaction vessel, under the protection of protective gas, heating and stirring , Raise the temperature to 160°C, keep the reaction until the acid value is 45 ⁇ 1mg KOH/g, raise the temperature to 175°C, keep the reaction to the acid value 35 ⁇ 1mg KOH/g, raise the temperature to 200°C, and keep the reaction to the acid value 12 ⁇ 1mg KOH/g finishes the reaction; then, it is cooled to room temperature, the remaining raw materials are added, and the reaction is mixed to prepare the thermally conductive insulating paint.
- Example 1 It is basically the same as Application Example 1, except that the modified carbon nanotube prepared in Example 1 is added in an amount of 8 parts.
- the specific preparation method is as follows: Weigh each raw material according to the formula, and then add isophthalic anhydride, maleic anhydride, and 1,2-propanediol into the reaction vessel , Under the protection of protective gas, heat up and stir, heat up to 160°C, heat up the reaction to an acid value of 45 ⁇ 1mg KOH/g, heat up to 175°C, heat up the reaction to an acid value of 35 ⁇ 1mg KOH/g, heat up to 200°C , Heat preservation reaction to an acid value of 12 ⁇ 1 mg KOH/g to complete the reaction; then cool to room temperature, add the remaining raw materials, mix and react to prepare the thermally conductive insulating paint.
- Example 2 It is basically the same as Application Example 1, except that the modified carbon nanotubes are prepared in Example 2.
- the viscosity is tested directly with insulating paint according to the standard.
- the electrical strength, volume resistivity, and dielectric loss tangent value are prepared according to the standard of 1mm thickness paint.
- the curing process 140°C, 2h; 160°C, 6h.
- Thermal conductivity According to the standard, the length and width are 10mm ⁇ 10mm, and the thickness is 1mm.
- the curing process 140°C, 2h; 160°C, 6h.
- the bonding strength is prepared according to the standard of the spiral coil.
- the preparation process is to put the spiral coil into the paint for 10 minutes, take it out and put it in a 140°C oven for 2h; then put the spiral coil into the paint in the reverse direction and put it into the oven at 140°C, 2h; 160°C , 6h.
- Heat resistance index is prepared according to the standard with a thickness of 5mm, and the curing process: 140°C, 2h; 160°C, 6h.
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Abstract
Disclosed in the present invention are a preparation method for a modified carbon nanotube and use thereof, the preparation method comprising: (1) preparing a surface-carboxylated carbon nanotube; and (2) dissolving the surface-carboxylated carbon nanotube in a mixed solution of water and ethanol, then adding tetraethoxysilane, vinyltriethoxysilane and aqueous ammonia, reacting same to prepare the modified carbon nanotube, the surface of the modified carbon nanotube having a vinyl group. Further disclosed is use of the modified carbon nanotube prepared by the preparation method in a thermally conductive and insulating material. The modified carbon nanotube prepared by the preparation method of the present invention can have the characteristics of high thermal conductivity, low electrical conductivity, and good compatibility with organics; and is thus especially suitable for a thermally conductive and insulating paint.
Description
本申请要求申请号为:CN 201911170322.X、申请日为2019.11.26的中国国家知识产权局的在先专利申请为优先权,该在先专利申请文本中的内容通过引用而完全加入本专利申请中。This application requires the prior patent application of the State Intellectual Property Office of China with the application number of CN 201911170322.X and the filing date of 2019.11.26 as priority, and the content of the prior patent application text is fully incorporated into this patent application by reference in.
本发明属于导热绝缘技术领域,具体地涉及一种改性碳纳米管的制备方法及其的应用。The invention belongs to the technical field of thermal conductivity and insulation, and specifically relates to a method for preparing modified carbon nanotubes and applications thereof.
随着电机技术的不断发展,电机功率不断提升,电机的功耗也同时提升,这导致电机的工作温度越来越高,而其中电机各部件尤其是绝缘件的散热能力直接影响着电机的温升,如果电机温升超过限值,会导致绝缘老化、线圈击穿、电机烧毁,而绝缘漆如果同时具有高导热性能和电气绝缘性能,就可以有效地降低电机绕组温升,从而能够增大电机的输出力,而现有技术中的绝缘漆仍然存在难以兼具优异的导热性、绝缘性以及机械力学性能的问题,使得电机的质量与寿命等等受到了极大地限制。因此现有技术中对绝缘漆的要求也越来越高,为了解决以上问题,一般有两个思路,一是不断提升绝缘漆的耐热等级,以适应电机的高工作温度;二是提高绝缘漆的导热性能,提升电机的散热性,从而降低电机的工作温度。相对于提高耐热等级,提升绝缘漆的导热性有着可以降低电机能耗,提升电机整体寿命等优点而被重点关注。With the continuous development of motor technology, the power of the motor is continuously increasing, and the power consumption of the motor is also increasing at the same time, which causes the working temperature of the motor to become higher and higher, and the heat dissipation capacity of the motor components, especially the insulating parts, directly affects the temperature of the motor. If the motor temperature rise exceeds the limit, it will cause insulation aging, coil breakdown, and motor burnout. If the insulating varnish has both high thermal conductivity and electrical insulation performance, it can effectively reduce the temperature rise of the motor windings, thereby increasing The output power of the motor, and the insulating paint in the prior art still has the problem that it is difficult to have excellent thermal conductivity, insulation and mechanical properties, which greatly limits the quality and life of the motor. Therefore, the requirements for insulating paint in the prior art are getting higher and higher. In order to solve the above problems, there are generally two ideas. One is to continuously improve the heat resistance level of the insulating paint to adapt to the high working temperature of the motor; the other is to improve the insulation. The thermal conductivity of the paint improves the heat dissipation of the motor, thereby reducing the working temperature of the motor. Compared with improving the heat resistance level, improving the thermal conductivity of the insulating paint has the advantages of reducing the energy consumption of the motor and improving the overall life of the motor.
然而现今绝大部分绝缘漆因为使用高分子材料,导热性能都比较差,为了提升绝缘漆的导热性能,大部分的研究者都使用掺杂高导热材料的方法,但这些绝缘漆为了获得高导热性一般都需要高掺杂,而高掺杂将影响绝缘漆的其它机械力学性能,同时还存在面临掺杂粒子与绝缘漆相容性差等问题。例如不饱和聚酯树脂,由于其生产工艺简单、原料易得、耐化学腐蚀、力学性能和电学性能优良、可常温固化、良好的工艺性能等优点,进而作为热固性树脂中用量最大的品种而被广泛应用于绝缘漆中,但其同样存在上述问题,为了提升导热性而加入高掺杂的填充导热材料,一方面由于分散不均匀或者导热材料本身的缺陷难以实现较好的导热,另一方面,由于导热材料与有机物表界面不相容性进一步限制了其导热功效的发挥。However, most insulating varnishes nowadays have poor thermal conductivity due to the use of polymer materials. In order to improve the thermal conductivity of insulating varnishes, most researchers use the method of doping with high thermal conductivity materials, but these insulating varnishes are in order to obtain high thermal conductivity. In general, high doping is required for performance, and high doping will affect other mechanical properties of insulating varnish, and there are also problems such as poor compatibility of doped particles with insulating varnish. For example, unsaturated polyester resin, due to its simple production process, easy availability of raw materials, chemical corrosion resistance, excellent mechanical and electrical properties, room temperature curing, good process performance, etc., and then used as the largest variety of thermosetting resins. It is widely used in insulating paint, but it also has the above problems. In order to improve the thermal conductivity, adding highly doped thermally conductive materials, on the one hand, it is difficult to achieve better heat conduction due to uneven dispersion or the defects of the thermally conductive material itself, on the other hand , Due to the incompatibility of the thermal conductive material and the surface interface of the organic matter further restricts its thermal conductivity.
其中导热材料中的碳纳米管(CNTs)材料因为它卓越的导热、力学强度、导电等性能而受到了广泛的关注,根据麦克斯韦尔的混合理论,添加1%的碳纳米管,理论上可以提升有机物50倍的导热率,因此有望解决上述提及高掺杂带来的负面影响,例如高掺杂降低了绝缘漆的力学性能等性能;然而对于绝缘材料来说,又由于碳纳米管具有 高的导电率以及与有机物表界面不相容性限制了碳纳米管作为导热材料在绝缘材料中的应用。Among them, carbon nanotubes (CNTs) in thermal conductive materials have received extensive attention because of their excellent thermal conductivity, mechanical strength, electrical conductivity and other properties. According to Maxwell’s mixing theory, adding 1% of carbon nanotubes can theoretically improve The thermal conductivity of organic compounds is 50 times, so it is expected to solve the negative effects of high doping mentioned above. For example, high doping reduces the mechanical properties of insulating varnishes; however, for insulating materials, carbon nanotubes have high The high electrical conductivity and incompatibility with the surface and interface of organic matter limit the application of carbon nanotubes as thermally conductive materials in insulating materials.
发明内容Summary of the invention
本发明的目的在于克服现有技术的不足,提供一种新的改性碳纳米管的制备方法,该制备方法制备的改性碳纳米管能够兼具高导热、低导电、与有机物相容性好的特性。The purpose of the present invention is to overcome the shortcomings of the prior art and provide a new method for preparing modified carbon nanotubes. The modified carbon nanotubes prepared by the method can combine high thermal conductivity, low electrical conductivity, and compatibility with organics. Good characteristics.
本发明同时还提供了一种上述方法制备的改性碳纳米管在导热绝缘材料中的应用。The invention also provides an application of the modified carbon nanotube prepared by the above method in a thermally conductive insulating material.
为解决上述技术问题,本发明采取如下技术方案:To solve the above technical problems, the present invention adopts the following technical solutions:
一种改性碳纳米管的制备方法,所述制备方法包括如下步骤:A preparation method of modified carbon nanotubes, the preparation method includes the following steps:
(1)制备表面羧酸化的碳纳米管;(1) Preparation of carbon nanotubes with surface carboxylation;
(2)将步骤(1)制备的所述表面羧酸化的碳纳米管溶解在水和乙醇的混合溶液中,然后加入正硅酸乙酯、乙烯基三乙氧基硅烷和氨水,反应,制成所述改性碳纳米管,所述改性碳纳米管表面具有乙烯基。(2) The surface carboxylated carbon nanotubes prepared in step (1) are dissolved in a mixed solution of water and ethanol, and then ethyl orthosilicate, vinyl triethoxysilane and ammonia are added to react to prepare The modified carbon nanotube is formed, and the surface of the modified carbon nanotube has a vinyl group.
根据本发明,所述制备方法制成的所述改性碳纳米管包括碳纳米管核层与形成在所述碳纳米管核层表面的二氧化硅壳层,所述碳纳米管核层与所述二氧化硅壳层之间部分或全部通过化学键连接。According to the present invention, the modified carbon nanotube produced by the preparation method includes a carbon nanotube core layer and a silica shell layer formed on the surface of the carbon nanotube core layer, the carbon nanotube core layer and Part or all of the silica shell layers are connected by chemical bonds.
根据本发明的一些优选方面,步骤(2)中,所述反应在30-50℃下进行。According to some preferred aspects of the present invention, in step (2), the reaction is carried out at 30-50°C.
根据本发明的一些优选方面,步骤(2)中,所述正硅酸乙酯、所述乙烯基三乙氧基硅烷和所述氨水分别采用滴加的形式加入混合溶液中。According to some preferred aspects of the present invention, in step (2), the ethyl orthosilicate, the vinyl triethoxy silane and the ammonia are added to the mixed solution in the form of dropwise addition.
根据本发明的一些具体且优选的方面,步骤(2)中,所述正硅酸乙酯、所述乙烯基三乙氧基硅烷和所述氨水加入混合溶液的步骤具体如下:首先将所述正硅酸乙酯与所述乙烯基三乙氧基硅烷的混合物中的部分滴加至混合溶液中,同时滴加部分所述氨水,反应;然后分别加入剩余部分的所述混合物和所述氨水。According to some specific and preferred aspects of the present invention, in step (2), the step of adding the ethyl orthosilicate, the vinyl triethoxysilane and the ammonia water to the mixed solution is specifically as follows: Part of the mixture of ethyl orthosilicate and the vinyl triethoxy silane is added dropwise to the mixed solution, while a part of the ammonia water is added dropwise to react; then the remaining part of the mixture and the ammonia water are added separately .
根据本发明的一些优选方面,步骤(2)中,所述表面羧酸化的碳纳米管、所述正硅酸乙酯和所述乙烯基三乙氧基硅烷的混合物、所述氨水的投料质量比为1∶0.9-1.2∶1-1.2。According to some preferred aspects of the present invention, in step (2), the feed quality of the surface carboxylated carbon nanotubes, the mixture of the ethyl orthosilicate and the vinyl triethoxysilane, and the ammonia The ratio is 1:0.9-1.2:1-1.2.
根据本发明的一些优选方面,步骤(2)中,所述水与所述乙醇的投料质量比为1∶0.95-1.1。According to some preferred aspects of the present invention, in step (2), the feed mass ratio of the water to the ethanol is 1:0.95-1.1.
根据本发明的一些优选方面,步骤(2)中,控制所述正硅酸乙酯和所述乙烯基三乙氧基硅烷中的一个相对于另一个的投料质量比在3倍以内。According to some preferred aspects of the present invention, in step (2), the feed mass ratio of one of the ethyl orthosilicate and the vinyl triethoxysilane relative to the other is controlled to be within 3 times.
根据本发明的一些具体且优选的方面,步骤(1)中,所述表面羧酸化的碳纳米管通过将碳纳米管与混合酸在105-115℃下混合反应制成,所述混合酸由硫酸和硝酸构成。According to some specific and preferred aspects of the present invention, in step (1), the surface carboxylated carbon nanotubes are prepared by mixing and reacting carbon nanotubes with a mixed acid at 105-115°C, and the mixed acid is made of Consists of sulfuric acid and nitric acid.
根据本发明的一些具体且优选的方面,所述硫酸与所述硝酸的投料质量比为2-4∶1。According to some specific and preferred aspects of the present invention, the feed mass ratio of the sulfuric acid to the nitric acid is 2-4:1.
根据本发明的一些具体且优选的方面,所述碳纳米管为多壁碳纳米管和/或单壁碳纳米管。According to some specific and preferred aspects of the present invention, the carbon nanotubes are multi-wall carbon nanotubes and/or single-wall carbon nanotubes.
本发明中,硫酸的质量分数为80-98%,硝酸的质量分数为60-80%。In the present invention, the mass fraction of sulfuric acid is 80-98%, and the mass fraction of nitric acid is 60-80%.
本发明提供的又一技术方案:一种上述所述的改性碳纳米管的制备方法制成的改性碳纳米管在导热绝缘材料中的应用。Another technical solution provided by the present invention: an application of modified carbon nanotubes produced by the above-mentioned method for preparing modified carbon nanotubes in thermally conductive insulating materials.
由于以上技术方案的实施,本发明与现有技术相比具有如下优点:Due to the implementation of the above technical solutions, the present invention has the following advantages compared with the prior art:
本发明创新地采用特定方法制成表面含有乙烯基的改性碳纳米管,而且由于制成的改性碳纳米管核层与壳层之间具有化学键连接,使得本发明的改性碳纳米管能够稳定存在并能够以较少的添加量应用于绝缘漆,且能以乙烯键参与到绝缘漆不饱和树脂的交联网络中,使得制成的绝缘漆不仅能够兼具优异的导热性和绝缘性,而且还能够获得优异的机械力学性能,克服了现有技术中高掺杂存在的不利于普通浸渍工艺以及VPI浸渍工艺的缺陷,耐温等级能够达到H级。The present invention innovatively adopts a specific method to prepare modified carbon nanotubes with vinyl on the surface, and because the prepared modified carbon nanotubes have a chemical bond between the core layer and the shell layer, the modified carbon nanotubes of the present invention It can exist stably and can be applied to insulating varnish with a small amount of addition, and can participate in the cross-linking network of the unsaturated resin of insulating varnish with vinyl bonds, so that the insulating varnish made can not only have excellent thermal conductivity and insulation It can also obtain excellent mechanical properties, overcome the disadvantages of high doping in the prior art that are not conducive to the common impregnation process and the VPI impregnation process, and the temperature resistance level can reach H level.
随着电机技术的不断发展,电机功率不断提升,电机的功耗也同时提升,这导致电机的工作温度越来越高,而其中电机各部件尤其是绝缘件的散热能力直接影响着电机的温升,如果电机温升超过限值,会导致绝缘老化、线圈击穿、电机烧毁,而绝缘漆如果同时具有高导热性能和电气绝缘性能,就可以有效地降低电机绕组温升,从而能够增大电机的输出力,而现有技术中的绝缘漆仍然存在难以兼具优异的导热性、绝缘性以及机械力学性能的问题,使得电机的质量与寿命等等受到了极大地限制。With the continuous development of motor technology, the power of the motor is continuously increasing, and the power consumption of the motor is also increasing at the same time, which causes the working temperature of the motor to become higher and higher, and the heat dissipation capacity of the motor components, especially the insulating parts, directly affects the temperature of the motor. If the motor temperature rise exceeds the limit, it will cause insulation aging, coil breakdown, and motor burnout. If the insulating varnish has both high thermal conductivity and electrical insulation performance, it can effectively reduce the temperature rise of the motor windings, thereby increasing The output power of the motor, and the insulating paint in the prior art still has the problem that it is difficult to have excellent thermal conductivity, insulation and mechanical properties, which greatly limits the quality and life of the motor.
基于上述问题,本发明提供一种由特定方法制成的特定结构的改性碳纳米管,其使得改性碳纳米管以核壳结构存在,在碳纳米管核层的表面形成二氧化硅壳层,同时使得两层之间以化学键连接,使得结合更紧密更牢固,有利于充分发挥碳纳米管的导热性而抑制碳纳米管的导电性,而且还赋予了改性碳纳米管的表面乙烯基,使得改性碳纳米管能够参与到有机树脂例如不饱和聚酯树脂的交联网络中,从而一方面能够确保碳纳米管在绝缘漆中均匀分散,充分利用其导热性,而且还提升了树脂固化的交联度,另一方面,使得本发明的碳纳米管能够以较少的添加量应用于绝缘漆中,进而不影响绝缘漆的机械力学性能以及电性能。Based on the above problems, the present invention provides a modified carbon nanotube with a specific structure made by a specific method, which allows the modified carbon nanotube to exist in a core-shell structure, and a silica shell is formed on the surface of the carbon nanotube core layer. At the same time, the two layers are connected by a chemical bond to make the bond tighter and stronger, which is conducive to giving full play to the thermal conductivity of carbon nanotubes and inhibiting the conductivity of carbon nanotubes, and also gives the modified carbon nanotube surface ethylene Base, so that the modified carbon nanotubes can participate in the crosslinking network of organic resins such as unsaturated polyester resins, so that on the one hand, it can ensure that the carbon nanotubes are evenly dispersed in the insulating paint, make full use of their thermal conductivity, and also improve The degree of crosslinking of the resin curing, on the other hand, enables the carbon nanotubes of the present invention to be applied to insulating paint with a small amount of addition, and thus does not affect the mechanical properties and electrical properties of the insulating paint.
具体地,本申请提供的一种改性碳纳米管的制备方法,包括:(1)制备表面羧酸化的碳纳米管;(2)将步骤(1)制备的所述表面羧酸化的碳纳米管溶解在水和乙醇的混合溶液中,然后加入正硅酸乙酯、乙烯基三乙氧基硅烷和氨水,反应,制成所述改性碳纳米管,所述改性碳纳米管表面具有乙烯基。根据本发明,制成的所述改性碳纳米管包括碳纳米管核层与形成在所述碳纳米管核层表面的二氧化硅壳层,所述碳纳米管核层与所述二氧化硅壳层之间部分或全部通过化学键连接。Specifically, a method for preparing modified carbon nanotubes provided by the present application includes: (1) preparing surface carboxylated carbon nanotubes; (2) preparing the surface carboxylated carbon nanotubes prepared in step (1) The tube is dissolved in a mixed solution of water and ethanol, and then ethyl orthosilicate, vinyl triethoxy silane and ammonia are added to react to form the modified carbon nanotube, the surface of the modified carbon nanotube has Vinyl. According to the present invention, the modified carbon nanotube produced includes a carbon nanotube core layer and a silica shell layer formed on the surface of the carbon nanotube core layer, the carbon nanotube core layer and the dioxide Part or all of the silicon shell layers are connected by chemical bonds.
以下结合具体实施例对本发明做进一步详细说明。应理解,这些实施例用于说明本发明的基本原理、主要特征和优点,而本发明不受以下实施例的限制。实施例中采用的实施条件可以根据具体要求做进一步调整,未注明的实施条件通常为常规实验中的条件。实施例所用原料均为可商购的工业品。The present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that these embodiments are used to illustrate the basic principles, main features and advantages of the present invention, but the present invention is not limited by the following embodiments. The implementation conditions used in the examples can be further adjusted according to specific requirements, and implementation conditions not specified are usually conditions in routine experiments. The raw materials used in the examples are all commercially available industrial products.
下述实施例中,如无特殊说明,所有的原料基本来自于商购或者通过本领域的常规方法制备而得。下述中,浓硫酸的质量百分数为98%,硝酸的质量百分数为68%,氨水的质量百分数为28%,多壁碳纳米管购自(北京德科岛金科技有限公司,CNT106)。In the following examples, unless otherwise specified, all raw materials are basically commercially available or prepared by conventional methods in the art. In the following, the mass percentage of concentrated sulfuric acid is 98%, the mass percentage of nitric acid is 68%, the mass percentage of ammonia is 28%, and the multi-walled carbon nanotubes are purchased from (Beijing Deke Island Gold Technology Co., Ltd., CNT106).
实施例1改性碳纳米管的制备Example 1 Preparation of modified carbon nanotubes
(1)制备表面羧酸化的碳纳米管;将1份多壁碳纳米管加入90份浓硫酸中超声分散30分钟,再在这份溶液中加入30份硝酸,并在110℃油浴下搅拌6小时。反应完成后,将这份溶液倒入1000份水中,得到黄褐色溶液,再将这份溶液以10000r/min的速度离心分离,将产物水洗后继续离心三次,得到表面羧酸化的碳纳米管;(1) Prepare surface carboxylated carbon nanotubes; add 1 part of multi-walled carbon nanotubes to 90 parts of concentrated sulfuric acid to ultrasonically disperse for 30 minutes, then add 30 parts of nitric acid to this solution, and stir at 110°C in an oil bath 6 hours. After the reaction is completed, pour the solution into 1000 parts of water to obtain a yellowish-brown solution, and then centrifuge the solution at a speed of 10000r/min, wash the product with water and continue centrifugation three times to obtain carbon nanotubes with carboxylated surface;
(2)将步骤(1)制备的10份表面羧酸化的碳纳米管加入50份水和50份乙醇的混合液中,将5份正硅酸乙酯和5份乙烯基三乙氧基硅烷混合,并准备10份氨水。将表面羧酸化的碳纳米管溶液放入35℃油浴中搅拌,缓慢滴加10份正硅酸乙酯与乙烯基三乙氧基硅烷混合液中的1份,在滴加上述混合液的同时缓慢滴加1份氨水,滴加完毕后搅拌30分钟;然后缓慢将剩余9份正硅酸乙酯与乙烯基三乙氧基硅烷混合液以及9份氨水滴加完,滴加完成后反应2小时,后用10000r/min转速离心分离,得到改性碳纳米管。(2) Add 10 parts of surface carboxylated carbon nanotubes prepared in step (1) to a mixture of 50 parts of water and 50 parts of ethanol, and add 5 parts of ethyl orthosilicate and 5 parts of vinyl triethoxy silane Mix and prepare 10 parts ammonia. Place the carboxylated carbon nanotube solution in an oil bath at 35°C and stir, slowly add 1 part of the mixture of 10 parts of ethyl orthosilicate and vinyl triethoxy silane, and then add dropwise to the above mixture. At the same time, slowly add 1 part of ammonia water, and stir for 30 minutes after the addition is complete; then slowly add the remaining 9 parts of ethyl orthosilicate and vinyl triethoxy silane mixture and 9 parts of ammonia dropwise. After the dripping is completed, the reaction After 2 hours, centrifuged at 10000r/min to obtain modified carbon nanotubes.
实施例2改性碳纳米管的制备Example 2 Preparation of modified carbon nanotubes
(1)制备表面羧酸化的碳纳米管;将1份多壁碳纳米管加入90份浓硫酸中超声分散30分钟,再在这份溶液中加入35份硝酸,并在115℃油浴下搅拌6小时,反应完成后,将这份溶液倒入1000份水中,得到黄褐色溶液,再将这份溶液以10000r/min的速度离心分离,将产物水洗后继续离心三次,得到表面羧酸化的碳纳米管;(1) Prepare surface carboxylated carbon nanotubes; add 1 part of multi-walled carbon nanotubes to 90 parts of concentrated sulfuric acid to ultrasonically disperse for 30 minutes, then add 35 parts of nitric acid to this solution, and stir at 115°C in an oil bath After 6 hours, after the reaction is complete, pour this solution into 1000 parts of water to obtain a yellow-brown solution, and then centrifuge this solution at a speed of 10000r/min. After washing the product with water, continue centrifugation three times to obtain surface carboxylated carbon. nanotube;
(2)将步骤(1)制备的10份表面羧酸化的碳纳米管加入50份水和50份乙醇的混合液中,将2.5份正硅酸乙酯和7.5份乙烯基三乙氧基硅烷混合,并准备10份氨水。将表面羧酸化的碳纳米管溶液放入40℃油浴中搅拌,缓慢滴加10份正硅酸乙酯与乙烯基三乙氧基硅烷混合液中的1份,在滴加上述混合液的同时缓慢滴加1份氨水,滴加完毕后搅拌30分钟;然后缓慢将剩余9份正硅酸乙酯与乙烯基三乙氧基硅烷混合液以及9份氨水滴加完,滴加完成后反应2小时,后用10000r/min转速离心分离,得到改性碳纳米管。(2) Add 10 parts of carbon nanotubes with surface carboxylation prepared in step (1) to a mixture of 50 parts of water and 50 parts of ethanol, and add 2.5 parts of ethyl orthosilicate and 7.5 parts of vinyl triethoxy silane Mix and prepare 10 parts ammonia. Place the carboxylated carbon nanotube solution in an oil bath at 40°C and stir, slowly add 1 part of the mixture of 10 parts of ethyl orthosilicate and vinyl triethoxysilane, and then add dropwise to the above mixture. At the same time, slowly add 1 part of ammonia water, and stir for 30 minutes after the addition is complete; then slowly add the remaining 9 parts of ethyl orthosilicate and vinyl triethoxy silane mixture and 9 parts of ammonia dropwise. After the dripping is completed, the reaction After 2 hours, centrifuged at 10000r/min to obtain modified carbon nanotubes.
实施例3改性碳纳米管的制备Example 3 Preparation of modified carbon nanotubes
(1)制备表面羧酸化的碳纳米管;将1份多壁碳纳米管加入90份浓硫酸中超声分散30分钟,再在这份溶液中加入30份硝酸,并在110℃油浴下搅拌6小时。反应完成后,将这份溶液倒入1000份水中,得到黄褐色溶液,再将这份溶液以10000r/min的速度离心分离,将产物水洗后继续离心三次,得到表面羧酸化的碳纳米管;(1) Prepare surface carboxylated carbon nanotubes; add 1 part of multi-walled carbon nanotubes to 90 parts of concentrated sulfuric acid to ultrasonically disperse for 30 minutes, then add 30 parts of nitric acid to this solution, and stir at 110°C in an oil bath 6 hours. After the reaction is completed, pour the solution into 1000 parts of water to obtain a yellowish-brown solution, and then centrifuge the solution at a speed of 10000r/min, wash the product with water and continue centrifugation three times to obtain carbon nanotubes with carboxylated surface;
(2)将步骤(1)制备的10份表面羧酸化的碳纳米管加入50份水和50份乙醇的混合液中,将7.5份正硅酸乙酯和2.5份乙烯基三乙氧基硅烷混合,并准备10份氨水。将表面羧酸化的碳纳米管溶液放入35℃油浴中搅拌,缓慢滴加10份正硅酸乙酯与乙烯基三乙氧基硅烷混合液中的1份,在滴加上述混合液的同时缓慢滴加1份氨水,滴加完毕后搅拌30分钟;然后缓慢将剩余9份正硅酸乙酯与乙烯基三乙氧基硅烷混合液以及9份氨水滴加完,滴加完成后反应2小时,后用10000r/min转速离心分离,得到改性碳纳米管。(2) Add 10 parts of surface carboxylated carbon nanotubes prepared in step (1) to a mixture of 50 parts of water and 50 parts of ethanol, and add 7.5 parts of ethyl orthosilicate and 2.5 parts of vinyl triethoxy silane Mix and prepare 10 parts ammonia. Place the carboxylated carbon nanotube solution in an oil bath at 35°C and stir, slowly add 1 part of the mixture of 10 parts of ethyl orthosilicate and vinyl triethoxy silane, and then add dropwise to the above mixture. At the same time, slowly add 1 part of ammonia water, and stir for 30 minutes after the addition is complete; then slowly add the remaining 9 parts of ethyl orthosilicate and vinyl triethoxy silane mixture and 9 parts of ammonia dropwise. After the dripping is completed, the reaction After 2 hours, centrifuged at 10000r/min to obtain modified carbon nanotubes.
对比例1Comparative example 1
基本同实施例1,其区别仅在于:将“5份正硅酸乙酯和5份乙烯基三乙氧基硅烷”替换为10份的正硅酸乙酯。It is basically the same as Example 1, except that: "5 parts of ethyl orthosilicate and 5 parts of vinyl triethoxysilane" are replaced with 10 parts of ethyl orthosilicate.
对比例2Comparative example 2
基本同实施例1,其区别仅在于:将“5份正硅酸乙酯和5份乙烯基三乙氧基硅烷”替换为10份的乙烯基三乙氧基硅烷。It is basically the same as Example 1, except that: "5 parts of ethyl orthosilicate and 5 parts of vinyl triethoxy silane" are replaced with 10 parts of vinyl triethoxy silane.
应用实施例1Application Example 1
本例提供一种导热绝缘漆,以质量份数计,所述导热绝缘漆的原料包括:间苯二甲酸酐10份,顺丁烯二酸酐22份,1,2-丙二醇23.6份,实施例1制备的改性碳纳米管4份,过氧化二苯甲酰1份,环烷酸钴0.05份,苯乙烯23份,对苯二酚0.02份。This example provides a thermally conductive insulating paint. In parts by mass, the raw materials of the thermally conductive insulating paint include: 10 parts of isophthalic anhydride, 22 parts of maleic anhydride, and 23.6 parts of 1,2-propylene glycol. Examples 1. Prepare 4 parts of modified carbon nanotubes, 1 part of dibenzoyl peroxide, 0.05 parts of cobalt naphthenate, 23 parts of styrene, and 0.02 parts of hydroquinone.
其制备方法如下:按配方称取各原料,然后将间苯二甲酸酐、顺丁烯二酸酐、1,2-丙二醇、改性碳纳米管加入反应容器中,在保护气体保护下,升温搅拌,升温至160℃,保温反应至酸值为45±1mg KOH/g,升温至175℃,保温反应至酸值为35±1mg KOH/g,升温至200℃,保温反应至酸值12±1mg KOH/g结束反应;然后冷却至室温,加入剩余原料,混合反应,制得所述导热绝缘漆。The preparation method is as follows: Weigh the raw materials according to the formula, then add isophthalic anhydride, maleic anhydride, 1,2-propanediol, and modified carbon nanotubes into the reaction vessel, under the protection of protective gas, heating and stirring , Raise the temperature to 160°C, keep the reaction until the acid value is 45±1mg KOH/g, raise the temperature to 175°C, keep the reaction to the acid value 35±1mg KOH/g, raise the temperature to 200°C, and keep the reaction to the acid value 12±1mg KOH/g finishes the reaction; then, it is cooled to room temperature, the remaining raw materials are added, and the reaction is mixed to prepare the thermally conductive insulating paint.
应用实施例2Application Example 2
基本同应用实施例1,区别仅在于:实施例1制备的改性碳纳米管的添加量为2份。It is basically the same as Application Example 1, except that the modified carbon nanotubes prepared in Example 1 are added in 2 parts.
应用实施例3Application Example 3
基本同应用实施例1,区别仅在于:实施例1制备的改性碳纳米管的添加量为8份。It is basically the same as Application Example 1, except that the modified carbon nanotube prepared in Example 1 is added in an amount of 8 parts.
应用实施例4Application Example 4
基本同应用实施例1,区别仅在于制备方法不同,具体的制备方法如下:按配方称取各原料,然后将间苯二甲酸酐、顺丁烯二酸酐、1,2-丙二醇加入反应容器中,在保 护气体保护下,升温搅拌,升温至160℃,保温反应至酸值为45±1mg KOH/g,升温至175℃,保温反应至酸值为35±1mg KOH/g,升温至200℃,保温反应至酸值12±1mg KOH/g结束反应;然后冷却至室温,加入剩余原料,混合反应,制得所述导热绝缘漆。It is basically the same as Application Example 1, except that the preparation method is different. The specific preparation method is as follows: Weigh each raw material according to the formula, and then add isophthalic anhydride, maleic anhydride, and 1,2-propanediol into the reaction vessel , Under the protection of protective gas, heat up and stir, heat up to 160°C, heat up the reaction to an acid value of 45±1mg KOH/g, heat up to 175°C, heat up the reaction to an acid value of 35±1mg KOH/g, heat up to 200°C , Heat preservation reaction to an acid value of 12±1 mg KOH/g to complete the reaction; then cool to room temperature, add the remaining raw materials, mix and react to prepare the thermally conductive insulating paint.
应用实施例5Application Example 5
基本同应用实施例1,区别仅在于:改性碳纳米管采用实施例2制备的。It is basically the same as Application Example 1, except that the modified carbon nanotubes are prepared in Example 2.
应用实施例6Application Example 6
基本同应用实施例1,区别仅在于:改性碳纳米管采用实施例3制备的。It is basically the same as Application Example 1, except that the modified carbon nanotubes are prepared in Example 3.
应用对比例1Application Comparative Example 1
基本同应用实施例1,区别仅在于:改性碳纳米管采用对比例1制备的。It is basically the same as Application Example 1, except that the modified carbon nanotubes are prepared by using Comparative Example 1.
应用对比例2Application Comparative Example 2
基本同应用实施例1,区别仅在于:改性碳纳米管采用对比例2制备的。It is basically the same as Application Example 1, except that the modified carbon nanotubes are prepared by using Comparative Example 2.
性能测试Performance Testing
将上述应用实施例1-6以及应用对比例1-2所制得的导热绝缘漆进行如下一些性能测试,具体结果参见表1。The following performance tests were performed on the thermally conductive insulating varnishes prepared in the application examples 1-6 and the application comparative examples 1-2 as follows, and the specific results are shown in Table 1.
粘度按标准用绝缘漆直接测试。电气强度、体积电阻率、介电损耗正切值按标准制备1mm厚度漆片,固化工艺:140℃,2h;160℃,6h。导热系数按标准制备长、宽10mm×10mm,厚1mm导热片,固化工艺:140℃,2h;160℃,6h。粘结强度按标准制备螺旋线圈,制备工艺,将螺旋线圈正向投入漆中10min,取出后放入140℃烘箱2h;再将螺旋线圈反向投入漆中放入烘箱140℃,2h;160℃,6h。耐热指数按标准制备厚度为5mm的样条,固化工艺:140℃,2h;160℃,6h。The viscosity is tested directly with insulating paint according to the standard. The electrical strength, volume resistivity, and dielectric loss tangent value are prepared according to the standard of 1mm thickness paint. The curing process: 140℃, 2h; 160℃, 6h. Thermal conductivity: According to the standard, the length and width are 10mm×10mm, and the thickness is 1mm. The curing process: 140℃, 2h; 160℃, 6h. The bonding strength is prepared according to the standard of the spiral coil. The preparation process is to put the spiral coil into the paint for 10 minutes, take it out and put it in a 140℃ oven for 2h; then put the spiral coil into the paint in the reverse direction and put it into the oven at 140℃, 2h; 160℃ , 6h. Heat resistance index is prepared according to the standard with a thickness of 5mm, and the curing process: 140℃, 2h; 160℃, 6h.
表1Table 1
由上表可知,本发明在导热绝缘漆中即使是只添加2份例如应用实施例2,仍然能够获得较理想的导热系数,而应用对比例1虽然添加了4份,但是效果反而不如本发明;其中,应用对比例2虽然获得了较好的导热系数,但是其电性能较差,不利于应用在绝缘材料中。It can be seen from the above table that even if only 2 parts are added to the thermally conductive insulating varnish of the present invention, for example, application example 2, it can still obtain a more ideal thermal conductivity. However, although 4 parts are added in application comparative example 1, the effect is not as good as the present invention. ; Among them, although the application of Comparative Example 2 has obtained a better thermal conductivity, but its electrical properties are poor, which is not conducive to application in insulating materials.
上述实施例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围,凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。The above-mentioned embodiments are only to illustrate the technical concept and features of the present invention, and their purpose is to enable those skilled in the art to understand the content of the present invention and implement them accordingly, and should not limit the scope of protection of the present invention. The equivalent changes or modifications made by the spirit essence should all be covered within the protection scope of the present invention.
Claims (10)
- 一种改性碳纳米管的制备方法,其特征在于,所述制备方法包括如下步骤:A preparation method of modified carbon nanotubes, characterized in that, the preparation method includes the following steps:(1)制备表面羧酸化的碳纳米管;(1) Preparation of carbon nanotubes with surface carboxylation;(2)将步骤(1)制备的所述表面羧酸化的碳纳米管溶解在水和乙醇的混合溶液中,然后加入正硅酸乙酯、乙烯基三乙氧基硅烷和氨水,反应,制成所述改性碳纳米管,所述改性碳纳米管表面具有乙烯基。(2) The surface carboxylated carbon nanotubes prepared in step (1) are dissolved in a mixed solution of water and ethanol, and then ethyl orthosilicate, vinyl triethoxysilane and ammonia are added to react to prepare The modified carbon nanotube is formed, and the surface of the modified carbon nanotube has a vinyl group.
- 根据权利要求1所述的改性碳纳米管的制备方法,其特征在于,所述制备方法制成的所述改性碳纳米管包括碳纳米管核层与形成在所述碳纳米管核层表面的二氧化硅壳层,所述碳纳米管核层与所述二氧化硅壳层之间部分或全部通过化学键连接。The method for preparing modified carbon nanotubes according to claim 1, wherein the modified carbon nanotubes produced by the preparation method comprise a carbon nanotube core layer and a carbon nanotube core layer formed on the carbon nanotube core layer. On the surface of the silica shell layer, the carbon nanotube core layer and the silica shell layer are partially or completely connected by chemical bonds.
- 根据权利要求1或2所述的改性碳纳米管的制备方法,其特征在于,步骤(2)中,所述反应在30-50℃下进行。The method for preparing modified carbon nanotubes according to claim 1 or 2, characterized in that, in step (2), the reaction is carried out at 30-50°C.
- 根据权利要求1或2所述的改性碳纳米管的制备方法,其特征在于,步骤(2)中,所述正硅酸乙酯、所述乙烯基三乙氧基硅烷和所述氨水分别采用滴加的形式加入混合溶液中。The method for preparing modified carbon nanotubes according to claim 1 or 2, wherein in step (2), the ethyl orthosilicate, the vinyl triethoxy silane and the ammonia water are respectively Add to the mixed solution in the form of dropwise addition.
- 根据权利要求4所述的改性碳纳米管的制备方法,其特征在于,步骤(2)中,所述正硅酸乙酯、所述乙烯基三乙氧基硅烷和所述氨水加入混合溶液的步骤具体如下:首先将所述正硅酸乙酯与所述乙烯基三乙氧基硅烷的混合物中的部分滴加至混合溶液中,同时滴加部分所述氨水,反应;然后分别加入剩余部分的所述混合物和所述氨水。The method for preparing modified carbon nanotubes according to claim 4, wherein in step (2), the ethyl orthosilicate, the vinyl triethoxy silane and the ammonia are added to the mixed solution The specific steps are as follows: firstly, the part of the mixture of the ethyl orthosilicate and the vinyl triethoxy silane is added dropwise to the mixed solution, while a part of the ammonia water is added dropwise to react; then the remaining parts are added separately Part of the mixture and the ammonia water.
- 根据权利要求1或2所述的改性碳纳米管的制备方法,其特征在于,步骤(2)中,所述表面羧酸化的碳纳米管、所述正硅酸乙酯和所述乙烯基三乙氧基硅烷的混合物、所述氨水的投料质量比为1∶0.9-1.2∶1-1.2;和/或,步骤(2)中,所述水与所述乙醇的投料质量比为1∶0.95-1.1。The method for preparing modified carbon nanotubes according to claim 1 or 2, wherein in step (2), the surface carboxylated carbon nanotubes, the ethyl orthosilicate and the vinyl group The feed mass ratio of the mixture of triethoxysilane and the ammonia water is 1:0.9-1.2:1-1.2; and/or, in step (2), the feed mass ratio of the water to the ethanol is 1: 0.95-1.1.
- 根据权利要求1或2所述的改性碳纳米管的制备方法,其特征在于,步骤(2)中,控制所述正硅酸乙酯和所述乙烯基三乙氧基硅烷中的一个相对于另一个的投料质量比在3倍以内。The method for preparing modified carbon nanotubes according to claim 1 or 2, wherein in step (2), one of the ethyl orthosilicate and the vinyl triethoxysilane is controlled to be relatively The feed mass ratio to the other is within 3 times.
- 根据权利要求1或2所述的改性碳纳米管的制备方法,其特征在于,步骤(1)中,所述表面羧酸化的碳纳米管通过将碳纳米管与混合酸在105-115℃下混合反应制成,所述混合酸由硫酸和硝酸构成。The method for preparing modified carbon nanotubes according to claim 1 or 2, wherein in step (1), the surface carboxylated carbon nanotubes are heated by mixing the carbon nanotubes with a mixed acid at 105-115°C. The mixed acid is made by the lower mixing reaction, and the mixed acid is composed of sulfuric acid and nitric acid.
- 根据权利要求8所述的改性碳纳米管的制备方法,其特征在于,所述硫酸与所述硝酸的投料质量比为2-4∶1;和/或,所述碳纳米管为多壁碳纳米管和/或单壁碳纳米管。The method for preparing modified carbon nanotubes according to claim 8, wherein the feed mass ratio of the sulfuric acid to the nitric acid is 2-4:1; and/or, the carbon nanotubes are multi-walled Carbon nanotubes and/or single-walled carbon nanotubes.
- 一种权利要求1-9中任一项权利要求所述的改性碳纳米管的制备方法制成的改性碳纳米管在导热绝缘材料中的应用。An application of modified carbon nanotubes made by the method for preparing modified carbon nanotubes according to any one of claims 1-9 in a thermally conductive insulating material.
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