WO2020258621A1

WO2020258621A1 - High thermal conductivity modified epoxy resin and preparation method therefor

Info

Publication number: WO2020258621A1
Application number: PCT/CN2019/113891
Authority: WO
Inventors: 吴斌; 景录如; 崔益华; 张春琪; 薛建军; 徐晓风; 马俊锋
Original assignee: 苏州太湖电工新材料股份有限公司
Priority date: 2019-06-26
Filing date: 2019-10-29
Publication date: 2020-12-30
Also published as: CN111635493B; CN111635493A; CN110283284A; CN110283284B

Abstract

Disclosed are a modified epoxy resin and a preparation method therefor. Raw materials comprise an epoxy resin, an ester-containing vinyl monomer, and a vinyl-containing hydrophobic hexagonal boron nitride nanosheet; the modified epoxy resin is prepared from the epoxy resin undergoing a polymerization reaction with the other raw materials. For the preparation of the vinyl-containing hydrophobic hexagonal boron nitride nanosheet: a surface hydroxyl modification and a freeze-thaw expansion treatment are employed, and then, combined with a specific compound of formula (I) in a one-pot synthesis, the stripping of boron nitride and the catalysis of an esterification modification are performed. The preparation method: a) preparing the vinyl-containing hydrophobic hexagonal boron nitride nanosheet; and b) allowing the epoxy resin, the vinyl-containing hydrophobic hexagonal boron nitride nanosheet prepared in step a), and the other raw materials to undergo the polymerization reaction under the presence of an initiator in a third solution, thus generating the modified epoxy resin. The modified epoxy resin of the present application has the advantages of high thermal conductivity, low dielectric loss, high electric field strength, increased mechanical strength, and additionally stable product quality between batches during preparation.

Description

一种高导热的改性环氧树脂及其制备方法Modified epoxy resin with high thermal conductivity and preparation method thereof

本申请要求2019年6月26日向中国国家知识产权局递交的申请号为201910559009.9的发明专利申请的优先权，该优先权文本内容明确通过援引加入并入本申请中。This application claims the priority of the invention patent application with application number 201910559009.9 filed with the State Intellectual Property Office of China on June 26, 2019. The content of the priority text is expressly incorporated into this application by reference.

技术领域Technical field

本申请属于高分子复合材料及电工技术领域，具体地涉及一种高导热的改性环氧树脂及其制备方法。The application belongs to the technical field of polymer composite materials and electrical engineering, and specifically relates to a modified epoxy resin with high thermal conductivity and a preparation method thereof.

背景技术Background technique

导热材料作为一种重要的功能材料被广泛的应用于国防事业和国民经济产业中。例如随着微电子集成技术和组装技术的快速发展，电子元器件和逻辑电路的体积越来越小，而工作频率急剧增加，半导体热环境向高温方向迅速变化，此时电子设备所产生的热量迅速积累、增加，在使用环境温度下，为保证电子元器件长时间高可靠性地正常工作，及时散热能力就成为影响其使用寿命的重要限制因素。又如大中型高压发电机的电动机在运行过程中产生的各种损耗均将转变成热能，使电机温升增高，温度升高是导致绝缘的电性能机械性能和寿命降低以及绝缘件松动的重要原因，如果不及时导出，将直接影响其工作效率，缩短寿命，降低其可靠性。因此，基于上述原因，目前迫切需要一种高导热性能的绝缘材料以解决上述问题。As an important functional material, thermal conductive materials are widely used in national defense and national economic industries. For example, with the rapid development of microelectronics integration technology and assembly technology, the volume of electronic components and logic circuits is getting smaller and smaller, and the operating frequency increases sharply, and the semiconductor thermal environment changes rapidly to high temperatures. At this time, the heat generated by electronic equipment Rapid accumulation and increase. In order to ensure the normal operation of electronic components with high reliability for a long time under the ambient temperature of use, timely heat dissipation capacity has become an important limiting factor affecting their service life. Another example is the large and medium-sized high-voltage generators. The various losses generated during the operation of the motor will be converted into heat, which will increase the temperature of the motor. The increase in temperature is important for the reduction of the electrical and mechanical properties of the insulation and the loss of the insulation. The reason, if it is not exported in time, it will directly affect its work efficiency, shorten its life and reduce its reliability. Therefore, based on the above reasons, there is an urgent need for an insulating material with high thermal conductivity to solve the above problems.

目前，填充型高导热绝缘高分子复合材料能够在一定程度上解决上述问题并得到了广泛应用与研究，其主要采用向聚合物中填充导热成分，导热填料为高导热的无机材料，具有较高的导热系数，价格低廉，工艺简单，易于工业化生产，是目前高导热绝缘高分子复合材料研究的主要方向。而其中环氧树脂具有优越的绝缘性能，因此其作为重要的绝缘介质被广泛应用于电力绝缘设备中，而电力设备小型化和大功率化会产生越来多的热量，这对传统的绝缘材料提出了新的挑战。同时智能电网的建设也迫切需要高导热能力的绝缘材料。但是，环氧树脂的导热能力很差，其热导率只有0.17-0.21w/mk，为了提高环氧树脂的导热能力，选用高热导率的无机填料填充环氧树脂制得填充型复合材料，是获得导热环氧树脂最为经济且高效的方法。然而，导热填料的热导率与树脂基体的热导率的比值过高时，导热填料与树脂基体界面结合处存在气孔、界面相等缺陷，导致界面处存在较大热阻，声子散射严重，影响材料传热，进而使得导热填料对环氧树脂复合材料热导率的贡献就大为减小。At present, filled high thermal conductivity insulating polymer composite materials can solve the above problems to a certain extent and have been widely used and researched. They mainly use thermally conductive components filled in polymers. The thermally conductive fillers are inorganic materials with high thermal conductivity. The thermal conductivity of high thermal conductivity, low price, simple process and easy industrial production are the main research directions of high thermal conductivity insulating polymer composite materials. Among them, epoxy resin has superior insulation properties, so it is widely used in power insulation equipment as an important insulation medium, and the miniaturization and high-power of power equipment will generate more and more heat, which is very important for traditional insulation materials. Presents new challenges. At the same time, the construction of smart grids urgently needs insulating materials with high thermal conductivity. However, the thermal conductivity of epoxy resin is very poor, and its thermal conductivity is only 0.17-0.21w/mk. In order to improve the thermal conductivity of epoxy resin, high thermal conductivity inorganic fillers filled with epoxy resin are used to prepare filled composite materials. It is the most economical and efficient way to obtain thermally conductive epoxy resin. However, when the ratio of the thermal conductivity of the thermally conductive filler to the thermal conductivity of the resin matrix is too high, there will be pores at the interface of the thermally conductive filler and the resin matrix, and the interface defects will result in a large thermal resistance at the interface and serious phonon scattering. Affect the heat transfer of the material, and thus the contribution of the thermally conductive filler to the thermal conductivity of the epoxy resin composite material is greatly reduced.

氮化硼(BN)由于其高导热率、优异的机械特性以及其电绝缘性能，是一种非常有前景的介电复合材料。对导热填料进行表面处理，改善环氧树脂基体与导热填料界面结合，减少界面热阻，是进一步提高环氧树脂基复合材料导热性能的重要研究途径。Boron nitride (BN) is a very promising dielectric composite material due to its high thermal conductivity, excellent mechanical properties and its electrical insulation properties. Surface treatment of thermally conductive fillers, improving the interface between epoxy resin matrix and thermally conductive fillers, and reducing interface thermal resistance are important research approaches to further improve the thermal conductivity of epoxy resin-based composites.

例如，现有的制备高导热环氧树脂的方法，Wattanakul等研究发现，无机填料BN经表面活性剂处理，可有效增加BN的表面润湿性以及填料与树脂基体间的界面附着力。与未经处理的BN填料相比，BN/EP(环氧树脂)复合材料的热导率由1.5W/(m·K)提升到2.69W/(m·K)。For example, in the existing method of preparing high thermal conductivity epoxy resin, Wattanakul et al. found that the inorganic filler BN treated with a surfactant can effectively increase the surface wettability of BN and the interface adhesion between the filler and the resin matrix. Compared with untreated BN fillers, the thermal conductivity of BN/EP (epoxy resin) composites has been increased from 1.5W/(m·K) to 2.69W/(m·K).

又如Liang等(IEEE 59th Electronic components and technology conference[C],2009:437～440.)将未经过任何表面处理的BN直接填充到环氧树脂中，研究发现当体积填充量为80wt％时，树脂基复合材料的热导率仅为3.35W/(m·K)；Chung等(Composites PartA,2001,32(12):1749～1757.)研究发现，硅烷偶联剂对填料BN进行表面功能化处理后，树脂基复合材料的导热性能得到大幅提升。当BN体积填充量为57％时，树脂基复合材料的热导率由5.27W/(m·K)跃升至10W/(m·K)，为未处理前复合材料的两倍。Another example is Liang et al. (IEEE 59th Electronic components and technology conference[C], 2009:437～440.) directly filled BN without any surface treatment into epoxy resin. The study found that when the volume filling amount is 80wt%, The thermal conductivity of resin-based composites is only 3.35W/(m·K); Chung et al. (Composites Part A, 2001, 32(12): 1749～1757.) found that the silane coupling agent performs surface function on filler BN After chemical treatment, the thermal conductivity of the resin-based composite material has been greatly improved. When the BN volume filling amount is 57%, the thermal conductivity of the resin matrix composite material jumps from 5.27W/(m·K) to 10W/(m·K), which is twice that of the untreated composite material.

又如Yung等(Journal of Applied Polymer Science,2007，3587～3591.)在环氧树脂中分别掺入两种不同粒径比且经过表面改性后的的六方氮化硼和立方氮化硼，观察填料表面改性对复合材料导热性能的影响。研究发现，当BN填充量的体积分数达到25.7％时，复合材料的导热系数最高，为19.0W/(m·K)。与直接掺入单一六方氮化硼相比，复合材料的导热性能提升2.17倍。In another example, Yung et al. (Journal of Applied Polymer Science, 2007, 3587～3591.) mixed two kinds of hexagonal boron nitride and cubic boron nitride with different particle size ratios and surface modification in epoxy resin. Observe the effect of filler surface modification on the thermal conductivity of composite materials. The study found that when the volume fraction of the BN filling amount reached 25.7%, the thermal conductivity of the composite was the highest, 19.0W/(m·K). Compared with the direct incorporation of single hexagonal boron nitride, the thermal conductivity of the composite material is increased by 2.17 times.

然而，虽然现有技术也实现了导热填料氮化硼对环氧树脂复合材料热导率的较大提升，但是现有的制备的高导热环氧树脂还存在如下一些问题：However, although the prior art has also achieved a large increase in the thermal conductivity of the epoxy resin composite material by the thermally conductive filler boron nitride, the existing high thermal conductivity epoxy resin still has the following problems:

(1)现有技术采用导热粒子填充改性环氧树脂用量很大，一般在50％以上，最少也要25％，大大限制了使用范围；(1) The existing technology uses a large amount of thermally conductive particles to fill the modified epoxy resin, generally more than 50%, and at least 25%, which greatly limits the scope of use;

(2)现有技术采用导热粒子填充改性环氧树脂时，均是对填料进行表面活化处理，然后添加到环氧基体中，但实际应用时极大概率地出现分散不均，且发生了沉降现象，影响了产品导热效率及机电性能，同时批次间产品质量不稳定。(2) When the prior art uses thermally conductive particles to fill the modified epoxy resin, the filler is surface-activated and then added to the epoxy matrix. However, in actual applications, uneven dispersion and occurrence of The sedimentation phenomenon affects the thermal conductivity and electromechanical performance of the product, and the quality of the product between batches is unstable.

因此，本领域的技术人员亟待寻求一种解决上述问题的方式方法。Therefore, those skilled in the art urgently need to find a way to solve the above problems.

申请内容Application content

本申请的目的在于克服现有技术的不足，提供一种改进的高导热的改性环氧树脂，其在具有高导热系数、低介电损耗、高电场强度及较高的机械强度的基础上兼具制备时批次间产品质量稳定等优点。The purpose of this application is to overcome the shortcomings of the prior art and provide an improved modified epoxy resin with high thermal conductivity, which has high thermal conductivity, low dielectric loss, high electric field strength and high mechanical strength. It has the advantages of stable product quality between batches during preparation.

本申请同时还提供了上述高导热的改性环氧树脂的制备方法。The application also provides a method for preparing the above-mentioned modified epoxy resin with high thermal conductivity.

为解决上述技术问题，本申请采取如下一种技术方案：To solve the above technical problems, this application adopts the following technical solution:

一种改性环氧树脂，所述改性环氧树脂的原料包括环氧树脂，所述原料还包括含有酯基的乙烯基单体、含有乙烯基的疏水型六方氮化硼纳米片，所述改性环氧树脂由所述环氧树脂与剩余原料发生聚合反应制成；其中，所述含有乙烯基的疏水型六方氮化硼纳米片通过如下方法制备而得：A modified epoxy resin. The raw material of the modified epoxy resin includes epoxy resin, and the raw material further includes a vinyl monomer containing an ester group and a hydrophobic hexagonal boron nitride nanosheet containing a vinyl group. The modified epoxy resin is made by the polymerization reaction of the epoxy resin and the remaining raw materials; wherein the hydrophobic hexagonal boron nitride nanosheets containing vinyl groups are prepared by the following method:

(1)将六方氮化硼进行表面羟基化改性制备羟基化六方氮化硼；(1) Surface hydroxylation modification of hexagonal boron nitride to prepare hydroxylated hexagonal boron nitride;

(2)将步骤(1)制备的羟基化六方氮化硼进行冻融膨胀处理制备膨胀的羟基化六方氮化硼；(2) subjecting the hydroxylated hexagonal boron nitride prepared in step (1) to freeze-thaw expansion treatment to prepare expanded hydroxylated hexagonal boron nitride;

(3)将步骤(2)制备的膨胀的羟基化六方氮化硼与式(Ⅰ)所示的化合物在第一溶剂中混合搅拌，得第一混合溶液，然后向所得的第一混合溶液中加入不饱和酸和/或不饱和酸酐、第二溶剂，反应，制成所述含有乙烯基的疏水型六方氮化硼纳米片；(3) The expanded hydroxylated hexagonal boron nitride prepared in step (2) and the compound represented by formula (I) are mixed and stirred in the first solvent to obtain a first mixed solution, and then added to the obtained first mixed solution Adding unsaturated acid and/or unsaturated acid anhydride and a second solvent to react to prepare the hydrophobic hexagonal boron nitride nanosheets containing vinyl groups;

其中，R ₀为C _1-6的烷基。

Wherein, R ₀ is a C _1-6 alkyl group.

根据本申请的一些优选方面，所述含有酯基的乙烯基单体为式(Ⅱ)所示的化合物：According to some preferred aspects of the present application, the vinyl monomer containing an ester group is a compound represented by formula (II):

式中，R ₁为C _1-10的烷基，R ₂、R ₃分别独立地为氢或C _1-10的烷基。C _1-10的烷基包括甲基、乙基、丙基、异丙基、丁基、戊基、异戊基、新戊基、己基等等。

In the formula, R ₁ is a C _1-10 alkyl group, and R ₂ and R ₃ are each independently hydrogen or a C _1-10 alkyl group. The C _1-10 alkyl group includes methyl, ethyl, propyl, isopropyl, butyl, pentyl, isopentyl, neopentyl, hexyl and the like.

根据本申请的一些具体方面，式(Ⅱ)中，R ₂与R ₃中至少有一个为氢。 According to some specific aspects of the present application, in formula (II), at least one of R ₂ and R ₃ is hydrogen.

根据本申请的一些优选且具体的方面，所述含有酯基的乙烯基单体为选自式(Ⅱ)所示的化合物中的至少两种。根据本申请的一个具体方面，所述含有酯基的乙烯基单体为甲基丙烯酸甲酯(MAA)与丙烯酸丁酯(BA)的组合物。According to some preferred and specific aspects of the present application, the vinyl monomer containing an ester group is at least two selected from the compounds represented by formula (II). According to a specific aspect of the present application, the vinyl monomer containing an ester group is a combination of methyl methacrylate (MAA) and butyl acrylate (BA).

根据本申请的一些优选方面，所述环氧树脂为双酚型环氧树脂。According to some preferred aspects of the present application, the epoxy resin is a bisphenol epoxy resin.

根据本申请的一些优选且具体的方面，所述环氧树脂为选自式(Ⅲ)所示的化合物中的一种或多种的组合：According to some preferred and specific aspects of the present application, the epoxy resin is a combination of one or more selected from the compounds represented by formula (III):

(Ⅲ)，式中：R ₄为-C(CH ₃) ₂-、-CH ₂-或-S(O) ₂-，n为选自0-10的整数，即n可以为0、1、2、3、 4、5、6、7、8、9或10。根据本申请的一个具体方面，所述环氧树脂为环氧树脂E-51和/或环氧树脂E-44。 (Ⅲ), where: R ₄ is -C(CH ₃ ) ₂ -, -CH ₂ -or -S(O) ₂ -, n is an integer selected from 0-10, that is, n can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. According to a specific aspect of the present application, the epoxy resin is epoxy resin E-51 and/or epoxy resin E-44.

根据本申请的一些优选方面，所述环氧树脂、所述含有乙烯基的疏水型六方氮化硼纳米片和所述含有酯基的乙烯基单体的投料质量比为1∶0.05-0.1∶0.15-0.4。更优选地，所述环氧树脂、所述含有乙烯基的疏水型六方氮化硼纳米片和所述含有酯基的乙烯基单体的投料质量比为1∶0.05-0.085∶0.18-0.32。According to some preferred aspects of the present application, the feed mass ratio of the epoxy resin, the hydrophobic hexagonal boron nitride nanosheets containing vinyl groups and the vinyl monomer containing ester groups is 1:0.05-0.1: 0.15-0.4. More preferably, the feed mass ratio of the epoxy resin, the hydrophobic hexagonal boron nitride nanosheets containing vinyl groups and the vinyl monomers containing ester groups is 1:0.05-0.085:0.18-0.32.

根据本申请的一些优选方面，使所述聚合反应在温度100-120℃下进行。更优选地，使所述聚合反应在温度105-115℃下进行。According to some preferred aspects of the present application, the polymerization reaction is carried out at a temperature of 100-120°C. More preferably, the polymerization reaction is carried out at a temperature of 105-115°C.

根据本申请的一些具体方面，步骤(1)中，所述羟基化六方氮化硼通过如下方法制备：将六方氮化硼与氢氧化钠水溶液混合，在温度90～150℃下搅拌反应，制成。According to some specific aspects of the present application, in step (1), the hydroxylated hexagonal boron nitride is prepared by the following method: mixing hexagonal boron nitride and sodium hydroxide aqueous solution, stirring and reacting at a temperature of 90-150°C to prepare to make.

根据本申请的一些具体方面，步骤(1)中，所述六方氮化硼采用商购的纯度大于等于99％、粒径约为2～5μm的产品。According to some specific aspects of the present application, in step (1), the hexagonal boron nitride is a commercially available product with a purity greater than or equal to 99% and a particle size of about 2-5 μm.

根据本申请的一些具体且优选的方面，步骤(1)中，所述温度通过油浴加热的方法实现。According to some specific and preferred aspects of the present application, in step (1), the temperature is achieved by an oil bath heating method.

根据本申请的一些具体方面，步骤(1)中，所述搅拌反应后还包括采用蒸馏水清洗的步骤，直至清洗为中性，烘干，制得所述羟基化六方氮化硼。According to some specific aspects of the present application, in step (1), after the stirring reaction, it further includes a step of washing with distilled water until the washing becomes neutral, and drying to obtain the hydroxylated hexagonal boron nitride.

根据本申请的一些优选方面，步骤(2)中，所述冻融膨胀处理的操作方式为：将步骤(1)制备的羟基化六方氮化硼配制成水溶液，将所得水溶液在第一设定温度下冷冻，然后解冻至第二设定温度，如此循环冷冻、解冻步骤多次，制成所述膨胀的羟基化六方氮化硼；其中，所述第一设定温度为-50～-5℃，所述第二设定温度为10-30℃。更优选地，所述第一设定温度为-45～-15℃，所述第二设定温度为18～28℃。According to some preferred aspects of the present application, in step (2), the operation of the freeze-thaw swelling treatment is: preparing the hydroxylated hexagonal boron nitride prepared in step (1) into an aqueous solution, and placing the resulting aqueous solution in the first setting Frozen at a temperature, and then thawed to a second set temperature, and repeated freezing and thawing steps in this way to prepare the expanded hydroxylated hexagonal boron nitride; wherein, the first set temperature is -50～-5 ℃, the second set temperature is 10-30℃. More preferably, the first set temperature is -45 to -15°C, and the second set temperature is 18 to 28°C.

根据本申请的一些具体方面，步骤(2)中，所述水溶液的质量分数为5～20％。According to some specific aspects of the present application, in step (2), the mass fraction of the aqueous solution is 5-20%.

根据本申请的一些具体方面，步骤(2)中，所述冷冻的处理时间为1～8h。According to some specific aspects of the present application, in step (2), the freezing processing time is 1-8h.

根据本申请的一些具体方面，步骤(2)中，所述循环的次数为4～12次。According to some specific aspects of the present application, in step (2), the number of cycles is 4-12 times.

根据本申请的一些具体且优选的方面，步骤(3)中，所述的R ₀可以为甲基、乙基、丙基、丁基或戊基。 According to some specific and preferred aspects of the present application, in step (3), the R ₀ can be methyl, ethyl, propyl, butyl or pentyl.

根据本申请的一些优选方面，步骤(3)中，所述混合搅拌在温度为60～78℃下进行。更优选地，步骤(3)中，所述混合搅拌在温度为65～75℃下进行。在本申请的一些具体实施方式中，所述混合搅拌可采用超声波进行，所述混合搅拌可在水浴加热下实现控制温度。According to some preferred aspects of the present application, in step (3), the mixing and stirring are performed at a temperature of 60-78°C. More preferably, in step (3), the mixing and stirring are performed at a temperature of 65 to 75°C. In some specific embodiments of the present application, the mixing and stirring may be performed by ultrasonic waves, and the mixing and stirring may be heated in a water bath to achieve temperature control.

根据本申请的一些优选方面，步骤(3)中，在所述第二溶剂中发生的所述反应在温度为80～120℃、惰性气体存在下进行。更优选地，步骤(3)中，在所述第二溶剂中发生的所述反应在温度为85～115℃下进行。其中，所述惰性气体包括氮气、氩气等。According to some preferred aspects of the present application, in step (3), the reaction in the second solvent is carried out at a temperature of 80 to 120° C. in the presence of an inert gas. More preferably, in step (3), the reaction in the second solvent is carried out at a temperature of 85-115°C. Wherein, the inert gas includes nitrogen, argon and the like.

根据本申请的一些优选方面，步骤(3)中，控制所述混合搅拌在无水环境中进行。在本申请的一些具体实施方式中，可采用回流分水的方式将原料以及环境中的水分分离进而实现混合搅拌在无水环境中进行。According to some preferred aspects of the present application, in step (3), the mixing and stirring are controlled to be performed in an anhydrous environment. In some specific embodiments of the present application, the raw material and the moisture in the environment can be separated by refluxing water to realize mixing and stirring in an anhydrous environment.

根据本申请的一些优选方面，步骤(3)中，所述式(Ⅰ)所示的化合物与所述膨胀的羟基化六方氮化硼的投料质量比为6～12∶1。According to some preferred aspects of the present application, in step (3), the mass ratio of the compound represented by the formula (I) to the expanded hydroxylated hexagonal boron nitride is 6-12:1.

根据本申请的一些优选方面，所述不饱和酸和/或不饱和酸酐与所述膨胀的羟基化六方氮化硼的投料质量比0.05～0.5∶1。According to some preferred aspects of the present application, the feed mass ratio of the unsaturated acid and/or unsaturated acid anhydride to the expanded hydroxylated hexagonal boron nitride is 0.05-0.5:1.

根据本申请的一些优选方面，步骤(3)中，所述第一溶剂为环己烷，所述第二溶剂为乙酸乙酯。According to some preferred aspects of the present application, in step (3), the first solvent is cyclohexane, and the second solvent is ethyl acetate.

根据本申请的一些优选方面，所述不饱和酸为亚油酸和/或甲基丙烯酸，所述不饱和酸酐为衣康酸酐和/或顺丁烯二酸酐。According to some preferred aspects of the present application, the unsaturated acid is linoleic acid and/or methacrylic acid, and the unsaturated acid anhydride is itaconic anhydride and/or maleic anhydride.

本申请提供的上述制备含有乙烯基的疏水型六方氮化硼纳米片的方法，有别于现有技术，其不仅能够实现氮化硼纳米片的剥片与疏水改性一锅法进行，无需分离中间体，同时还可实现式(Ⅰ)化合物的重复使用，实现含有乙烯基的疏水型六方氮化硼纳米片的高产率，且改性彻底，几乎没有未改性的氮化硼纳米片的存在，进而可以实现工业化的批量生产。The above-mentioned method for preparing hydrophobic hexagonal boron nitride nanosheets containing vinyl groups provided in this application is different from the prior art, and it can not only realize the one-pot method of stripping and hydrophobic modification of boron nitride nanosheets without separation It can also realize the repeated use of the compound of formula (I) at the same time, realize the high yield of the hydrophobic hexagonal boron nitride nanosheets containing vinyl, and the modification is thorough, and there is almost no unmodified boron nitride nanosheets. Exist, and then can achieve industrialized mass production.

本申请提供的又一技术方案：一种上述所述的改性环氧树脂的制备方法，所述制备方法包括如下步骤：Another technical solution provided by this application: a preparation method of the above-mentioned modified epoxy resin, the preparation method includes the following steps:

(a)制备含有乙烯基的疏水型六方氮化硼纳米片；(a) Preparation of hydrophobic hexagonal boron nitride nanosheets containing vinyl groups;

(b)使环氧树脂、步骤(a)制备的含有乙烯基的疏水型六方氮化硼纳米片以及剩余原料在引发剂存在下、在第三溶剂中发生聚合反应，生成所述改性环氧树脂。(b) The epoxy resin, the vinyl-containing hydrophobic hexagonal boron nitride nanosheets prepared in step (a), and the remaining raw materials are polymerized in the presence of an initiator in a third solvent to form the modified ring Oxy resin.

根据本申请的一些具体方面，步骤(b)中，所述引发剂为过氧化二苯甲酰(BPO)。According to some specific aspects of the present application, in step (b), the initiator is dibenzoyl peroxide (BPO).

根据本申请的一些具体方面，步骤(b)中，所述第三溶剂为正丁醇。According to some specific aspects of the present application, in step (b), the third solvent is n-butanol.

根据本申请的一些具体方面，制备所述改性环氧树脂的具体实施方式为：(i)将环氧树脂与第三溶剂及1/4的引发剂混合均匀，置于接有冷凝水管、氮气的四口烧瓶内，加入步骤(a)制备的含有乙烯基的疏水型六方氮化硼纳米片，油浴加热到85-95℃恒温10-60min；According to some specific aspects of this application, the specific implementation for preparing the modified epoxy resin is: (i) mix the epoxy resin with the third solvent and 1/4 of the initiator uniformly, and place them in the condensed water pipe, Into a nitrogen four-neck flask, add the hydrophobic hexagonal boron nitride nanosheets containing vinyl prepared in step (a), and heat the oil bath to 85-95°C for 10-60 minutes;

(ii)升温到100-120℃左右，并同时用恒压滴液漏斗滴加溶解有3/4的引发剂的含有酯基的乙烯基单体溶液，缓慢滴加，滴完后保温反应3-4h，然后减压蒸馏除去第三溶剂(可循环使用)，即得。(ii) The temperature is raised to about 100-120℃, and at the same time, a constant pressure dropping funnel is used to dropwise add a vinyl monomer solution containing 3/4 of the initiator dissolved in the ester group, and slowly drop it. After the drop is completed, the temperature is kept for reaction 3 -4h, then under reduced pressure distillation to remove the third solvent (recyclable), ready.

由于以上技术方案的实施，本申请与现有技术相比具有如下优点：Due to the implementation of the above technical solutions, this application has the following advantages compared with the prior art:

本申请创新地采用含有酯基的乙烯基单体与含有乙烯基的疏水型六方氮化硼纳米片对环氧树脂进行聚合反应改性，从而使得氮化硼纳米片与环氧树脂实现共价键连接，而且含有乙烯基的疏水型六方氮化硼纳米片的添加量极少(在5％左右)，有效解决了物理填充难以分散均匀以及出现沉降的问题，使得聚合反应改性后的改性环氧树脂在具有高导热系数、低介电损耗、高电场强度及较高的机械强度的基础上兼具制备时批次间产品质量稳定；This application innovatively uses vinyl monomers containing ester groups and hydrophobic hexagonal boron nitride nanosheets containing vinyl groups to polymerize and modify epoxy resins, so that the boron nitride nanosheets and epoxy resins are covalently modified. The addition amount of hydrophobic hexagonal boron nitride nanosheets containing vinyl groups is very small (about 5%), which effectively solves the problems of physical filling that is difficult to disperse uniformly and sedimentation, which makes the polymerization reaction modified. On the basis of high thermal conductivity, low dielectric loss, high electric field strength and high mechanical strength, the epoxy resin has stable product quality between batches during preparation;

同时由于现有技术中对氮化硼纳米片改性后得到的改性氮化硼纳米片粗产物中含有未改性的氮化硼纳米片且较难以实现有效地分离，致使采用现有技术中直接得到的改性氮化硼纳米片对环氧树脂改性后各方面性能均不理想，而本申请采用特定方法制备得含有乙烯基的疏水型六方氮化硼纳米片，具体采用表面羟基改性、冻融膨胀处理，再结合特定的式(Ⅰ)化合物进行的氮化硼的剥片、酯化改性的催化，一方面实现了一锅法进行剥片与疏水改性，无需分离中间体，同时还可重复使用式(Ⅰ)化合物，且产率高，极大地节约了成本，另一方面所得的含有乙烯基的疏水型六方氮化硼纳米片粗产物中纯度高，几乎没有未改性的氮化硼或氮化硼纳米片，进而可以在本申请改性环氧树脂的过程中直接使用，不会影响改性后的环氧树脂的各方面性能。At the same time, because the crude product of modified boron nitride nanosheets obtained by modifying boron nitride nanosheets in the prior art contains unmodified boron nitride nanosheets and it is difficult to achieve effective separation, the existing technology is adopted The modified boron nitride nanosheets directly obtained in the modified epoxy resin are unsatisfactory in all aspects. However, this application uses a specific method to prepare the hydrophobic hexagonal boron nitride nanosheets containing vinyl groups, specifically using surface hydroxyl groups. Modification, freeze-thaw expansion treatment, combined with the catalysis of boron nitride stripping and esterification modification with specific formula (I) compound, on the one hand, it realizes one-pot method for stripping and hydrophobic modification without separating intermediates At the same time, the compound of formula (I) can be reused, and the yield is high, which greatly saves the cost. On the other hand, the obtained crude product of the hydrophobic hexagonal boron nitride nanosheets containing vinyl has high purity, almost unchanged The flexible boron nitride or boron nitride nanosheets can then be used directly in the process of modifying the epoxy resin in the present application, without affecting all aspects of the properties of the modified epoxy resin.

附图说明Description of the drawings

图1为实施例3制备的含有乙烯基的疏水型六方氮化硼纳米片的透射电镜图(TEM)，其中左边与右边为不同放大倍数的图；Figure 1 is a transmission electron microscope (TEM) image of a hydrophobic hexagonal boron nitride nanosheet containing vinyl prepared in Example 3. The left and right sides are images of different magnifications;

图2为实施例3制备的含有乙烯基的疏水型六方氮化硼纳米片的原子力显微镜(AFM)图像；2 is an atomic force microscope (AFM) image of the hydrophobic hexagonal boron nitride nanosheets containing vinyl groups prepared in Example 3;

图3为实施例3制备的含有乙烯基的疏水型六方氮化硼纳米片的XRD谱图。3 is an XRD spectrum of the hydrophobic hexagonal boron nitride nanosheets containing vinyl groups prepared in Example 3. FIG.

具体实施方式Detailed ways

以下结合具体实施例对本申请做进一步详细说明。应理解，这些实施例用于说明本申请的基本原理、主要特征和优点，而本申请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。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。The application 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 application, and the present application is not limited by the following embodiments. The implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not specified are usually conditions in routine experiments. The raw materials used in the examples are all commercially available industrial products. In the following examples, unless otherwise specified, all raw materials are basically commercially available or prepared by conventional methods in the field.

实施例1Example 1

式(Ⅰa)所示化合物(即式(Ⅰ)中R ₀为丙基)的制备：称取15.8g(0.073mo1)N-丁基吡啶溴盐([bpy]Br)和8g(0.073mo1)(四氟硼酸钠)NaBF ₄于塑料洗瓶中，加入100mL丙酮作溶剂，磁力搅拌，在室温下冷凝回流，反应12h，静置，减压抽滤，弃去白色固体NaBr，得淡黄色澄清滤夜，向淡黄色澄清滤夜中加入100mL二氯甲烷，有白色沉淀析出，减压抽滤，滤夜经旋转蒸发浓缩，除去其中的丙酮和二氯甲烷，所得黄色油状液体在60℃下真空干燥8h，得产品式(Ⅰa)所示化合物[bpy]BF ₄13.8g，收率85.2％； Preparation of the compound represented by formula (Ia) (that is, R ₀ in formula (I) is propyl): Weigh 15.8g (0.073mol) N-butylpyridine bromide ([bpy]Br) and 8g (0.073mol) (Sodium tetrafluoroborate) NaBF ₄ in a plastic washing bottle, add 100mL acetone as solvent, magnetically stir, condense and reflux at room temperature, react for 12h, stand still, filter under reduced pressure, discard the white solid NaBr, and get light yellow and clear On the filter night, add 100 mL of dichloromethane to the light yellow clear filter night, a white precipitate precipitates out, vacuum filtration, the filter night is concentrated by rotary evaporation to remove the acetone and dichloromethane, the resulting yellow oily liquid is vacuum at 60°C After drying for 8 hours, 13.8 g of the compound [bpy]BF ₄ represented by formula (Ia) was obtained, with a yield of 85.2%;

实施例2Example 2

式(Ⅰb)所示化合物(即式(Ⅰ)中R ₀为甲基)的制备：将28.2g(0.15mol)溴代N-乙基吡啶加入盛有50mL丙酮的锥形瓶中，加入16.5g(0.15mol)NaBF ₄，室温下磁力搅拌10h，过滤，旋转蒸发，将易挥发的丙酮除去，真空干燥，得白色固体式(Ⅰb)所示化合物25.16g，收率86.5％，m.p.53.2～53.6℃； The preparation of the compound represented by formula (Ib) (that is, R ₀ in formula (I) is methyl): add 28.2g (0.15mol) of bromo N-ethylpyridine into an Erlenmeyer flask containing 50mL of acetone, and add 16.5 g(0.15mol) NaBF ₄ , magnetically stirred at room temperature for 10 hours, filtered, rotovapped to remove the volatile acetone, and dried in vacuum to obtain 25.16g of a white solid compound represented by formula (Ib), yield 86.5%, mp53.2 ～53.6℃;

实施例3Example 3

本例提供一种改性环氧树脂的制备方法及采用该方法制备得到的改性环氧树脂，所述改性环氧树脂的原料包括：环氧树脂E-51 80g、含有乙烯基的疏水型六方氮化硼纳米片(M-BNNSs)6g、甲基丙烯酸甲酯(MAA)13g、丙烯酸丁酯(BA)7g。制备过程中所采用的溶剂为第三溶剂-正丁醇25g，引发剂为过氧化二苯甲酰(BPO)4g。This example provides a method for preparing a modified epoxy resin and a modified epoxy resin prepared by the method. The raw materials of the modified epoxy resin include: epoxy resin E-51 80g, hydrophobic vinyl containing Type hexagonal boron nitride nanosheets (M-BNNSs) 6g, methyl methacrylate (MAA) 13g, and butyl acrylate (BA) 7g. The solvent used in the preparation process was 25 g of n-butanol, the third solvent, and 4 g of dibenzoyl peroxide (BPO) was the initiator.

其制备方法具体包括：The preparation method specifically includes:

(a)制备含有乙烯基的疏水型六方氮化硼纳米片：(a) Preparation of hydrophobic hexagonal boron nitride nanosheets containing vinyl groups:

(1)将六方氮化硼进行表面羟基化改性制备羟基化六方氮化硼，具体实施方式为：将50g六方氮化硼(hBN纯度≥99％，粒径2～5μm)加入到1000ml的三口反应瓶中，然后加入事先配制好的5mol/L的氢氧化钠水溶液中，于100℃左右油浴加热条件下机械搅拌10h，所得的混合物经多次用蒸馏水洗涤至滤液为中性，烘干后得到羟基化六方氮化硼(hBN-OH)49.5g；(1) Hexagonal boron nitride is modified by surface hydroxylation to prepare hydroxylated hexagonal boron nitride. The specific implementation is: adding 50g of hexagonal boron nitride (hBN purity ≥99%, particle size 2～5μm) to 1000ml Then add a pre-prepared 5mol/L sodium hydroxide aqueous solution to a three-necked reaction flask, and mechanically stir for 10 hours under oil bath heating at about 100°C. The resulting mixture is washed with distilled water several times until the filtrate is neutral. After drying, 49.5 g of hydroxylated hexagonal boron nitride (hBN-OH) is obtained;

(2)将步骤(1)制备的羟基化六方氮化硼进行冻融膨胀处理制备膨胀的羟基化六方氮化硼，具体实施方式为：将步骤(1)中制备的羟基化六方氮化硼(hBN-OH)产物配制成质量分数为10％的蒸馏水溶液，放入-25℃左右的冰柜中冷冻处理5h，再解冻至室温，如此冻融循环6次，得到膨胀的羟基化六方氮化硼(P-hBN-OH)49.1g，经测定其表面羟基数为0.0209mmol/g；(2) The hydroxylated hexagonal boron nitride prepared in step (1) is subjected to freeze-thaw expansion treatment to prepare expanded hydroxylated hexagonal boron nitride. The specific embodiment is: the hydroxylated hexagonal boron nitride prepared in step (1) (hBN-OH) The product is formulated into a distilled water solution with a mass fraction of 10%, placed in a freezer at about -25°C for 5 hours, and then thawed to room temperature. In this way, the freeze-thaw cycle is 6 times to obtain an expanded hydroxylated hexagonal nitride Boron (P-hBN-OH) 49.1g, the number of hydroxyl groups on the surface is determined to be 0.0209mmol/g;

(3)取步骤(2)制备的膨胀的羟基化六方氮化硼(P-hBN-OH)25g，环己烷250mL装入1000mL带有搅拌器、回流分水器的三口烧瓶中，加热至回流，***内的水分由回流的溶剂逐步脱除，待回流分水器中没有水蒸出，降温至80℃，加入上述制备的式(Ⅰa)所示化合物237g，并将反应器放入超声波清洗器中，控制水温在70℃左右，超声搅拌反应24h，然后加入亚油酸12g、乙酸乙酯50mL，通入氮气，加热升温至100℃左右，回流反应4h，降温至65℃，减压抽滤，滤饼用甲苯/丙酮(1:1体积比)混合液清洗两次，然后再过滤，加入到500mL的甲苯/异丙醇混合液中形成微纳米分散液，以8000r/min的转速离心处理，取上层悬浮液，过滤、烘干(140℃)得所述含有乙烯基的疏水型六方氮化硼纳米片M-BNNSs(式(Ⅳ-1))14.4g，收率为57.3％；(3) Take 25 g of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in step (2), and put 250 mL of cyclohexane into a 1000 mL three-necked flask with a stirrer and reflux trap, and heat to Reflux, the water in the system is gradually removed by the refluxing solvent. When there is no water in the reflux separator, the temperature is reduced to 80°C, and 237g of the compound represented by formula (Ia) prepared above is added, and the reactor is placed in ultrasonic In the washer, control the water temperature at about 70°C, ultrasonically stir the reaction for 24h, then add 12g of linoleic acid and 50mL of ethyl acetate, and then add nitrogen, heat to about 100°C, reflux for 4h, cool to 65°C, reduce pressure Suction filtration, the filter cake was washed twice with toluene/acetone (1:1 volume ratio) mixture, then filtered, and added to 500mL toluene/isopropanol mixture to form a micro-nano dispersion at a speed of 8000r/min Centrifugal treatment, take the upper suspension, filter and dry (140℃) to obtain the vinyl-containing hydrophobic hexagonal boron nitride nanosheets M-BNNSs (formula (IV-1)) 14.4g, the yield is 57.3% ；

【收率的计算方式为：[The calculation method of yield is:

：m _M-BNNSs所得含有乙烯基的疏水型六方氮化硼纳米片(M-BNNSs)质量g；：W _P-BNOH为膨胀的羟基化六方氮化硼(P-hBN-OH)质量g；n _P-BNOH：为膨胀的羟基化六方氮化硼(P-hBN-OH)表面羟基含量mmol/g；M _ma：改性剂(不饱和酸或不饱和酸酐)的分子量，本例中亚油酸：280.44g/mol，下述实施例计算方式相同】。 : _M M-BNNSs is the mass g of hydrophobic hexagonal boron nitride nanosheets (M-BNNSs) containing vinyl groups; W _P-BNOH is the mass g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH); n _P-BNOH : the surface hydroxyl content of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) mmol/g; M _ma : the molecular weight of the modifier (unsaturated acid or unsaturated anhydride), in this example Oleic acid: 280.44 g/mol, the calculation method is the same in the following examples].

测得产物的TEM图如图1(a)(b)(c)所示，在多孔碳网格上可见单个剥落的M-BNNSs的TEM图像，呈现出单层M-BNNSs的透明效果，并显示2-3μm的横向尺寸，采用HRTEM(高清透射电镜)图1(d)测得侧面少层M-BNNSs的卷曲叠加图像，这种卷曲是由于在200KV电镜测试环境所造成，并可清晰可见BNNS卷曲的层数为7层，证明本申请获得了单层或少层的M-BNNSs。如图2所示：显示了从乙醇/水分散体中沉积在云母衬底上的M-BNNSs的典型的原子力显微镜(AFM)图像，显示了3nm的片状高度，这也揭示了剥离的M-BNNSs的特性。测得其XRD图为原始六方氮化硼与含有乙烯基的疏水型六方氮化硼纳米片M-BNNSs的XRD对比图，图中所示衍射峰(002),(100),(101),(102),(004),(104),(110),(112)均与六方氮化硼XRD标准峰一致，也证明了剥离得到的含有乙烯基的疏水型六方氮化硼纳米片不含其它杂质。另外，由图我们可以看到(002)峰向小角方向有所移动，并且峰值相对增强，这些都说明了剥离之后的改性六方氮化硼(002)面暴露更多，且面间距变得更大，说明氮化硼己经得到很好剥离。The TEM image of the measured product is shown in Figure 1(a)(b)(c). The TEM image of a single exfoliated M-BNNSs can be seen on the porous carbon grid, showing the transparent effect of a single layer of M-BNNSs, and Displaying a horizontal size of 2-3μm, using HRTEM (High Definition Transmission Electron Microscope) Figure 1(d) to measure the side curled superimposed image of a few layers of M-BNNSs. This curling is caused by the 200KV electron microscope test environment and can be clearly seen The number of BNNS curled layers is 7 layers, which proves that this application has obtained single-layer or few-layer M-BNNSs. As shown in Figure 2: A typical atomic force microscope (AFM) image of M-BNNSs deposited on a mica substrate from an ethanol/water dispersion, showing a flake height of 3nm, which also reveals the exfoliated M -The characteristics of BNNSs. The measured XRD pattern is the XRD comparison pattern of the original hexagonal boron nitride and the hydrophobic hexagonal boron nitride nanosheets M-BNNSs containing vinyl. The diffraction peaks (002), (100), (101) are shown in the figure. (102), (004), (104), (110), (112) are consistent with the XRD standard peaks of hexagonal boron nitride, which also proves that the hydrophobic hexagonal boron nitride nanosheets containing vinyl do not contain Other impurities. In addition, from the figure, we can see that the (002) peak has shifted to the small angle direction, and the peak is relatively enhanced. These all indicate that the modified hexagonal boron nitride (002) surface after peeling is more exposed, and the surface spacing has become Larger, indicating that the boron nitride has been well stripped.

上述减压抽滤后的滤液经冷却至25℃以下，静置分层4h，下层液体(即式(Ⅰa)所示化合物所在)经简单的旋蒸处理后，可再次用作下一循环的剥片剂和催化剂，从而得到重复使用；静置分层后的上层为混合溶剂，经减压蒸馏处理后可以循环使用；The filtrate after the vacuum suction filtration is cooled to below 25°C and left to stand for 4 hours. The lower liquid (where the compound represented by formula (Ia) is located) can be used again for the next cycle after simple rotary evaporation. The tablet and catalyst are peeled off, so as to be reused; the upper layer after standing for layering is a mixed solvent, which can be recycled after being treated by vacuum distillation;

式(Ⅳ-1)的结构式示意如下，仅显示了氮化硼纳米片上的一个羟基与亚油酸反应后共价连接的示意结构，在氮化硼纳米片上的其它羟基也可以与亚油酸反应后共价连接：The structural formula of formula (IV-1) is as follows, which only shows the schematic structure of one hydroxyl group on the boron nitride nanosheets reacted with linoleic acid and covalently connected. Other hydroxyl groups on the boron nitride nanosheets can also be combined with linoleic acid. Covalent connection after reaction:

(b)制备改性环氧树脂(b) Preparation of modified epoxy resin

(b-1)将环氧树脂E-51与正丁醇及1/4的BPO混合均匀，置于接有冷凝水管、氮气的四口烧瓶内，加入上述制备的式(Ⅳ-1)所示的含有乙烯基的疏水型六方氮化硼纳米片(M-BNNSs)，油浴加热到90℃恒温30min；(b-1) Mix epoxy resin E-51 with n-butanol and 1/4 of BPO uniformly, place them in a four-necked flask connected with a condensate pipe and nitrogen, and add the formula (IV-1) prepared above Hydrophobic hexagonal boron nitride nanosheets (M-BNNSs) containing vinyl as shown, heated in an oil bath to 90°C for 30 minutes;

(b-2)升温到110℃左右，并同时用恒压滴液漏斗滴加溶解有3/4BPO引发剂的混合单体(MAA及BA)溶液，缓慢滴加30min左右，滴完后保温反应3-4h，然后减压蒸馏除去正丁醇(可循环使用)即得改性环氧树脂(式Ⅴ-1)108g，合成路线示意如下：(b-2) The temperature is raised to about 110℃, and at the same time, the mixed monomer (MAA and BA) solution with 3/4BPO initiator dissolved in a constant pressure dropping funnel is added dropwise, and the solution is slowly dropped for about 30 minutes, and the reaction is kept warm after the dropping After 3-4 hours, the n-butanol is removed by vacuum distillation (recyclable) to obtain 108g of modified epoxy resin (Formula V-1). The synthetic route is shown as follows:

x、y、z独立地为1～25之间的整数，n为选自0-10的整数；具体地，上述采用的E51环氧树脂的环氧值为0.51，那么此环氧树脂的平均分子量应为200/0.51＝392.16；

代表n的平均数，下述实施例中当采用E51环氧树脂时，n相同；

处同样可以共聚聚合单体MAA、BA以及上述制备的式(Ⅳ-1)所示的含有乙烯基的疏水型六方氮化硼纳米片(M-BNNSs)，上述仅示例性地在其中一处活性位接枝共聚，以表明本申请方法可将式(Ⅳ-1)所示的含有乙烯基的疏水型六方氮化硼纳米片(M-BNNSs)共聚接枝到环氧树脂分子上，实现了无机氮化硼对环氧的杂化增韧改性；同时式Ⅴ-1所示的改性环氧树脂中式(Ⅳ-1)所示的含有乙烯基的疏水型六方氮化硼纳米片、MAA及BA三个不分先后的共聚接枝到环氧树脂基体上，式Ⅴ-1中仅示例性地提供了一种接枝方式，同样地，下述实施例中均为示例性地给出含有乙烯基的疏水型六方氮化硼纳米片以及改性环氧树脂的示意结构。 x, y, and z are independently integers between 1-25, and n is an integer selected from 0-10; specifically, the epoxy value of the E51 epoxy resin used above is 0.51, then the average The molecular weight should be 200/0.51=392.16;

Represents the average number of n. In the following examples, when E51 epoxy resin is used, n is the same;

The monomers MAA, BA and the vinyl-containing hydrophobic hexagonal boron nitride nanosheets (M-BNNSs) represented by formula (IV-1) prepared above can also be copolymerized. The above is only exemplary in one of them. Active site graft copolymerization, to show that the method of this application can copolymerize the hydrophobic hexagonal boron nitride nanosheets (M-BNNSs) containing vinyl groups represented by formula (IV-1) to epoxy resin molecules. The hybrid toughening modification of epoxy with inorganic boron nitride; at the same time, the modified epoxy resin represented by formula V-1 and the hydrophobic hexagonal boron nitride nanosheets containing vinyl groups represented by formula (Ⅳ-1) , MAA and BA are copolymerized and grafted onto the epoxy resin matrix in no particular order. Formula V-1 only provides an exemplary grafting method. Similarly, the following embodiments are all exemplary The schematic structures of hydrophobic hexagonal boron nitride nanosheets containing vinyl groups and modified epoxy resins are given.

实施例4Example 4

本例提供一种改性环氧树脂的制备方法及采用该方法制备得到的改性环氧树脂，所述环氧树脂的原料包括：环氧树脂E-51 80g、含有乙烯基的疏水型六方氮化硼纳米片(M-BNNSs)6g、甲基丙烯酸甲酯(MAA)13g、丙烯酸丁酯(BA)7g。制备过程中虽采用的溶剂为第三溶剂-正丁醇25g，引发剂为过氧化二苯甲酰(BPO)4g。This example provides a method for preparing a modified epoxy resin and a modified epoxy resin prepared by the method. The raw material of the epoxy resin includes: epoxy resin E-51 80g, hydrophobic hexagonal containing vinyl Boron nitride nanosheets (M-BNNSs) 6g, methyl methacrylate (MAA) 13g, and butyl acrylate (BA) 7g. Although the solvent used in the preparation process is 25 g of n-butanol, the third solvent, and the initiator is 4 g of dibenzoyl peroxide (BPO).

其制备方法具体包括：The preparation method specifically includes:

(3)取步骤(2)制备的膨胀的羟基化六方氮化硼(P-hBN-OH)25g，环己烷250mL装入1000mL带有搅拌器、回流分水器的三口烧瓶中，加热至回流，***内的水分由回流的溶剂逐步脱除，待回流分水器中没有水蒸出，降温至80℃，加入上述制备的式(Ⅰb)所示化合物218g，并将反应器放入超声波清洗器中，控制水温在70℃左右，超声搅拌反应24h，然后加入亚油酸12g、乙酸乙酯50mL，通入氮气，加热升温至100℃左右，回流反应4h，降温至65℃，减压抽滤，滤饼用甲苯/丙酮(1:1体积比)混合液清洗两次，然后再过滤，加入到500mL的甲苯/异丙醇混合液中形成微纳米分散液，以8000r/min的转速离心处理，取上层悬浮液，过滤、烘干(140℃)得所述含有乙烯基的疏水型六方氮化硼纳米片M-BNNSs式(Ⅳ-1)14.5g，收率为57.7％；(3) Take 25 g of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in step (2), and put 250 mL of cyclohexane into a 1000 mL three-necked flask with a stirrer and reflux trap, and heat to Reflux, the water in the system is gradually removed by the refluxing solvent. When there is no water in the reflux separator, the temperature is lowered to 80°C, 218g of the compound represented by formula (Ib) prepared above is added, and the reactor is placed in ultrasonic In the washer, control the water temperature at about 70°C, ultrasonically stir the reaction for 24h, then add 12g of linoleic acid and 50mL of ethyl acetate, and then add nitrogen, heat to about 100°C, reflux for 4h, cool to 65°C, reduce pressure Suction filtration, the filter cake was washed twice with toluene/acetone (1:1 volume ratio) mixture, then filtered, and added to 500mL toluene/isopropanol mixture to form a micro-nano dispersion at a speed of 8000r/min Centrifugal treatment, take the upper suspension, filter and dry (140°C) to obtain the vinyl-containing hydrophobic hexagonal boron nitride nanosheets M-BNNSs formula (IV-1) 14.5g, the yield is 57.7%;

其仅显示了氮化硼纳米片上的一个羟基与亚油酸反应后共价连接的示意结构，在氮化硼纳米片上的其它羟基也可以与亚油酸反应后共价连接；

It only shows the schematic structure of one hydroxyl group on the boron nitride nanosheet reacted with linoleic acid and covalently connected. Other hydroxyl groups on the boron nitride nanosheet can also be covalently connected after reacting with linoleic acid;

(b)改性环氧树脂的制备：(b) Preparation of modified epoxy resin:

(b-2)升温到110℃左右，并同时用恒压滴液漏斗滴加溶解有3/4BPO引发剂的混合单体(MAA及BA)溶液，缓慢滴加3 0min左右，滴完后保温反应3-4h，然后减压蒸馏除去正丁醇(可循环使用)即得所述改性环氧树脂108.1g。(b-2) The temperature is raised to about 110℃, and at the same time, the mixed monomer (MAA and BA) solution with 3/4BPO initiator dissolved in a constant pressure dropping funnel is added dropwise, and the solution is slowly added dropwise for about 3 0min, and the temperature is kept after dripping. After reacting for 3-4 hours, then distilling under reduced pressure to remove the n-butanol (recyclable) to obtain 108.1 g of the modified epoxy resin.

实施例5Example 5

本例提供一种改性环氧树脂的制备方法及采用该方法制备得到的改性环氧树脂，所述改性环氧树脂的原料包括：环氧树脂E-44 85g、含有乙烯基的疏水型六方氮化硼纳米片(M-BNNSs)6g、甲基丙烯酸甲酯(MAA)13g、丙烯酸丁酯(BA)7g。制备过程中所采用的溶剂为第三溶剂-正丁醇25g，引发剂为过氧化二苯甲酰(BPO)4g。This example provides a method for preparing a modified epoxy resin and a modified epoxy resin prepared by the method. The raw material of the modified epoxy resin includes: epoxy resin E-44 85g, hydrophobic vinyl containing Type hexagonal boron nitride nanosheets (M-BNNSs) 6g, methyl methacrylate (MAA) 13g, and butyl acrylate (BA) 7g. The solvent used in the preparation process was 25 g of n-butanol, the third solvent, and 4 g of dibenzoyl peroxide (BPO) was the initiator.

其制备方法具体包括：The preparation method specifically includes:

(3)取步骤(2)制备的膨胀的羟基化六方氮化硼(P-hBN-OH)25g，环己烷250mL装入1000mL带有搅拌器、回流分水器的三口烧瓶中，加热至回流，***内的水分由回流的溶剂逐步脱除，待回流分水器中没有水蒸出，降温至80℃，加入上述制备的式(Ⅰa)所示化合物237g，并将反应器放入超声波清洗器中，控制水温在70℃左右，超声搅拌反应24h，然后加入甲基丙烯酸4g、乙酸乙酯50mL，通入氮气，加热升温至100℃左右，回流反应4h，降温至65℃，减压抽滤，滤饼用甲苯/丙酮(1:1体积比)混合液清洗两次，然后再过滤，加入到500mL的甲苯/异丙醇混合液中形成微纳米分散液，以8000r/min的转速离心处理，取上层悬浮液，过滤、烘干(140℃)得所述含有乙烯基的疏水型六方氮化硼纳米片M-BNNSs(式(Ⅳ-2))14.3g，收率为57.1％；(3) Take 25 g of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in step (2), and put 250 mL of cyclohexane into a 1000 mL three-necked flask with a stirrer and reflux trap, and heat to Reflux, the water in the system is gradually removed by the refluxing solvent. When there is no water in the reflux separator, the temperature is reduced to 80°C, and 237g of the compound represented by formula (Ia) prepared above is added, and the reactor is placed in ultrasonic In the washer, control the water temperature at about 70°C, ultrasonically stir the reaction for 24h, then add 4g of methacrylic acid and 50mL of ethyl acetate, and then add nitrogen, heat to about 100°C, reflux for 4h, cool to 65°C, reduce pressure Suction filtration, the filter cake was washed twice with toluene/acetone (1:1 volume ratio) mixture, then filtered, and added to 500mL toluene/isopropanol mixture to form a micro-nano dispersion at a speed of 8000r/min Centrifugal treatment, take the upper suspension, filter and dry (140°C) to obtain the vinyl-containing hydrophobic hexagonal boron nitride nanosheet M-BNNSs (formula (IV-2)) 14.3g, the yield is 57.1% ；

式(Ⅳ-2)的结构式示意如下，仅显示了氮化硼纳米片上的一个羟基与甲基丙烯酸反应后共价连接的示意结构，在氮化硼纳米片上的其它羟基也可以与甲基丙烯酸反应后共价连接：The structural formula of formula (IV-2) is as follows. It only shows the schematic structure of a hydroxyl group on the boron nitride nanosheet reacted with methacrylic acid and covalently connected. Other hydroxyl groups on the boron nitride nanosheet can also be connected with methacrylic acid. Covalent connection after reaction:

(b)制备改性环氧树脂：(b) Preparation of modified epoxy resin:

(b-1)将环氧树脂E-44与正丁醇及1/4的BPO混合均匀，置于接有冷凝水管、氮气的四口烧瓶内，加入上述制备的式(Ⅳ-2)所示的含有乙烯基的疏水型六方氮化硼纳米片(M-BNNSs)，油浴加热到90℃恒温30min；(b-1) Mix epoxy resin E-44 with n-butanol and 1/4 of BPO uniformly, place them in a four-necked flask connected with a condensed water pipe and nitrogen, and add the formula (IV-2) prepared above Hydrophobic hexagonal boron nitride nanosheets (M-BNNSs) containing vinyl as shown, heated in an oil bath to 90°C for 30 minutes;

(b-2)升温到110℃左右，并同时用恒压滴液漏斗滴加溶解有3/4BPO引发剂的混合单体(MAA及BA)溶液，缓慢滴加3 0min左右，滴完后保温反应3-4h，然后减压蒸馏除去正丁醇(可循环使用)即得所述改性环氧树脂(式Ⅴ-2)113.5g，合成路线示意如下：(b-2) The temperature is raised to about 110℃, and at the same time, the mixed monomer (MAA and BA) solution with 3/4BPO initiator dissolved in a constant pressure dropping funnel is added dropwise, and the solution is slowly added dropwise for about 3 0min, and the temperature is kept after dripping. After reacting for 3-4 hours, then distilling under reduced pressure to remove the n-butanol (recyclable) to obtain 113.5 g of the modified epoxy resin (Formula V-2). The synthetic route is as follows:

x、y、z独立地为1～25之间的数，n为选自0-10的整数；上述采用的E44环氧树脂的环氧值为0.44，那么此环氧树脂的平均分子量应为200/0.44＝454.55；

代表n的平均数，下述实施例中当采用E44环氧树脂时n相同。 x, y, z are independently numbers between 1-25, n is an integer selected from 0-10; the epoxy value of the E44 epoxy resin used above is 0.44, then the average molecular weight of the epoxy resin should be 200/0.44=454.55;

Represents the average number of n. In the following examples, n is the same when E44 epoxy resin is used.

实施例6Example 6

其制备方法具体包括：The preparation method specifically includes:

(3)取步骤(2)制备的膨胀的羟基化六方氮化硼(P-hBN-OH)25g，环己烷250mL装入1000mL带有搅拌器、回流分水器的三口烧瓶中，加热至回流，***内的水分由回流的溶剂逐步脱除，待回流分水器中没有水蒸出，降温至80℃，加入上述制备的式(Ⅰb)所示化合物218g，并将反应器放入超声波清洗器中，控制水温在70℃左右，超声搅拌反应24h，然后加入甲基丙烯酸4g、乙酸乙酯50mL，通入氮气，加热升温至100℃左右，回流反应4h，降温至65℃，减压抽滤，滤饼用甲苯/丙酮(1:1体积比)混合液清洗两次，然后再过滤，加入到500mL的甲苯/异丙醇混合液中形成微纳米分散液，以8000r/min的转速离心处理，取上层悬浮液，过滤、烘干(140℃)得所述含有乙烯基的疏水型六方氮化硼纳米片M-BNNSs(式(Ⅳ-2))14.5g，收率为57.9％；(3) Take 25 g of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in step (2), and put 250 mL of cyclohexane into a 1000 mL three-necked flask with a stirrer and reflux trap, and heat to Reflux, the water in the system is gradually removed by the refluxing solvent. When there is no water in the reflux separator, the temperature is lowered to 80°C, 218g of the compound represented by formula (Ib) prepared above is added, and the reactor is placed in ultrasonic In the washer, control the water temperature at about 70°C, ultrasonically stir the reaction for 24h, then add 4g of methacrylic acid and 50mL of ethyl acetate, and then add nitrogen, heat to about 100°C, reflux for 4h, cool to 65°C, reduce pressure Suction filtration, the filter cake was washed twice with toluene/acetone (1:1 volume ratio) mixture, then filtered, and added to 500mL toluene/isopropanol mixture to form a micro-nano dispersion at a speed of 8000r/min Centrifugal treatment, take the upper suspension, filter and dry (140℃) to obtain the vinyl-containing hydrophobic hexagonal boron nitride nanosheet M-BNNSs (formula (IV-2)) 14.5g, the yield is 57.9% ；

(b)制备改性环氧树脂：(b) Preparation of modified epoxy resin:

(b-2)升温到110℃左右，并同时用恒压滴液漏斗滴加溶解有3/4BPO引发剂的混合单体(MAA及BA)溶液，缓慢滴加3 0min左右，滴完后保温反应3-4h，然后减压蒸馏除去正丁醇(可循环使用)即得所述改性环氧树脂113.7g。(b-2) The temperature is raised to about 110℃, and at the same time, the mixed monomer (MAA and BA) solution with 3/4BPO initiator dissolved in a constant pressure dropping funnel is added dropwise, and the solution is slowly added dropwise for about 3 0min, and the temperature is kept after dripping. After reacting for 3-4 hours, and then distilling under reduced pressure to remove the n-butanol (recyclable), 113.7 g of the modified epoxy resin is obtained.

实施例7Example 7

其制备方法具体包括：The preparation method specifically includes:

(3)取步骤(2)制备的膨胀的羟基化六方氮化硼(P-hBN-OH)25g，环己烷250mL装入1000mL带有搅拌器、回流分水器的三口烧瓶中，加热至回流，***内的水分由回流的溶剂逐步脱除，待回流分水器中没有水蒸出，降温至80℃，加入上述制备的式(Ⅰa)所示化合物237g，并将反应器放入超声波清洗器中，控制水温在70℃左右，超声搅拌反应24h，然后加入衣康酸酐5g、乙酸乙酯50mL，通入氮气，加热升温至100℃左右，回流反应4h，降温至65℃，减压抽滤，滤饼用甲苯/丙酮(1:1体积比)混合液清洗两次，然后再过滤，加入到500mL的甲苯/异丙醇混合液中形成微纳米分散液，以8000r/min的转速离心处理，取上层悬浮液，过滤、烘干(140℃)得所述含有乙烯基的疏水型六方氮化硼纳米片M-BNNSs(式(Ⅳ-3))14.8g，收率为59.1％；式(Ⅳ-3)的结构式示意如下，仅显示了氮化硼纳米片上的一个羟基与衣康酸酐反应后共价连接的示意结构，在氮化硼纳米片上的其它羟基也可以与衣康酸酐反应后共价连接：

(3) Take 25 g of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in step (2), and put 250 mL of cyclohexane into a 1000 mL three-necked flask with a stirrer and reflux trap, and heat to Reflux, the water in the system is gradually removed by the refluxing solvent. When there is no water in the reflux separator, the temperature is reduced to 80°C, and 237g of the compound represented by formula (Ia) prepared above is added, and the reactor is placed in ultrasonic In the washer, control the water temperature at about 70°C, ultrasonically stir the reaction for 24 hours, then add 5 g of itaconic anhydride and 50 mL of ethyl acetate, and then add nitrogen, heat to about 100°C, reflux for 4 hours, cool to 65°C, and reduce pressure Suction filtration, the filter cake was washed twice with toluene/acetone (1:1 volume ratio) mixture, then filtered, and added to 500mL toluene/isopropanol mixture to form a micro-nano dispersion at a speed of 8000r/min Centrifugal treatment, take the upper suspension, filter and dry (140°C) to obtain 14.8 g of the vinyl-containing hydrophobic hexagonal boron nitride nanosheet M-BNNSs (formula (IV-3)), with a yield of 59.1% ; The structural formula of formula (IV-3) is as follows, which only shows the schematic structure of a hydroxyl group on the boron nitride nanosheets reacting with itaconic anhydride, and the other hydroxyl groups on the boron nitride nanosheets can also be connected with itaconic Covalent connection after acid anhydride reaction:

(b)制备改性环氧树脂：(b) Preparation of modified epoxy resin:

(b-1)将环氧树脂(E-51)与正丁醇及1/4的BPO混合均匀，置于接有冷凝水管、氮气的四口烧瓶内，加入上述制备的式(Ⅳ-3)所示的含有乙烯基的疏水型六方氮化硼纳米片(M-BNNSs)，油浴加热到90℃恒温30min；(b-1) Mix epoxy resin (E-51), n-butanol and 1/4 of BPO uniformly, place them in a four-necked flask connected with a condensed water pipe and nitrogen, and add the formula (Ⅳ-3) prepared above ) Shows the hydrophobic hexagonal boron nitride nanosheets (M-BNNSs) containing vinyl, heated in an oil bath to 90°C for 30 minutes;

(b-2)升温到110℃左右，并同时用恒压滴液漏斗滴加溶解有3/4BPO引发剂的混合单体(MAA及BA)溶液，缓慢滴加3 0min左右，滴完后保温反应3-4h，然后减压蒸馏除去正丁醇(可循环使用)即得所述改性环氧树脂(式Ⅴ-3)108.9g，合成路线示意如下：(b-2) The temperature is raised to about 110℃, and at the same time, the mixed monomer (MAA and BA) solution with 3/4BPO initiator dissolved in a constant pressure dropping funnel is added dropwise, and the solution is slowly added dropwise for about 3 0min, and the temperature is kept after dripping. After reacting for 3-4 hours, then distilling under reduced pressure to remove the n-butanol (recyclable) to obtain 108.9 g of the modified epoxy resin (Formula V-3). The synthetic route is as follows:

x、y、z独立地为0～25之间的数且均不为0，n为选自0-10的整数；x, y, and z are independently numbers between 0-25 and none of them are 0, and n is an integer selected from 0-10;

实施例8Example 8

其制备方法具体包括：The preparation method specifically includes:

(3)取步骤(2)制备的膨胀的羟基化六方氮化硼(P-hBN-OH)25g，环己烷250mL装入1000mL带有搅拌器、回流分水器的三口烧瓶中，加热至回流，***内的水分由回流的溶剂逐步脱除，待回流分水器中没有水蒸出，降温至80℃，加入上述制备的式(Ⅰb)所示化合物218g，并将反应器放入超声波清洗器中，控制水温在70℃左右，超声搅拌反应24h，然后加入衣康酸酐5g、乙酸乙酯50mL，通入氮气，加热升温至100℃左右，回流反应4h，降温至65℃，减压抽滤，滤饼用甲苯/丙酮(1:1体积比)混合液清洗两次，然后再过滤，加入到500mL的甲苯/异丙醇混合液中形成微纳米分散液，以8000r/min的转速离心处理，取上层悬浮液，过滤、烘干(140℃)得所述含有乙烯基的疏水型六方氮化硼纳米片M-BNNSs(式(Ⅳ-3))14.7g，收率为58.7％；式(Ⅳ-3)的结构式示意如下，仅显示了氮化硼纳米片上的一个羟基与衣康酸酐反应后共价连接的示意结构，在氮化硼纳米片上的其它羟基也可以与衣康酸酐反应后共价连接：

(3) Take 25 g of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in step (2), and put 250 mL of cyclohexane into a 1000 mL three-necked flask with a stirrer and reflux trap, and heat to Reflux, the water in the system is gradually removed by the refluxing solvent. When there is no water in the reflux separator, the temperature is lowered to 80°C, 218g of the compound represented by formula (Ib) prepared above is added, and the reactor is placed in ultrasonic In the washer, control the water temperature at about 70°C, ultrasonically stir the reaction for 24 hours, then add 5 g of itaconic anhydride and 50 mL of ethyl acetate, and then add nitrogen, heat to about 100°C, reflux for 4 hours, cool to 65°C, and reduce pressure Suction filtration, the filter cake was washed twice with toluene/acetone (1:1 volume ratio) mixture, then filtered, and added to 500mL toluene/isopropanol mixture to form a micro-nano dispersion at a speed of 8000r/min Centrifugal treatment, take the upper suspension, filter and dry (140°C) to obtain 14.7 g of the vinyl-containing hydrophobic hexagonal boron nitride nanosheet M-BNNSs (formula (IV-3)), with a yield of 58.7% ; The structural formula of formula (IV-3) is as follows, which only shows the schematic structure of a hydroxyl group on the boron nitride nanosheets reacting with itaconic anhydride, and the other hydroxyl groups on the boron nitride nanosheets can also be connected with itaconic Covalent connection after acid anhydride reaction:

(b)制备改性环氧树脂：(b) Preparation of modified epoxy resin:

(b-2)升温到110℃左右，并同时用恒压滴液漏斗滴加溶解有3/4BPO引发剂的混合单体(MAA及BA)溶液，缓慢滴加3 0min左右，滴完后保温反应3-4h，然后减压蒸馏除去正丁醇(可循环使用)即得所述改性环氧树脂108.8g。(b-2) The temperature is raised to about 110℃, and at the same time, the mixed monomer (MAA and BA) solution with 3/4BPO initiator dissolved in a constant pressure dropping funnel is added dropwise, and the solution is slowly added dropwise for about 3 0min, and the temperature is kept after dripping. After reacting for 3-4 hours, then distilling under reduced pressure to remove the n-butanol (recyclable) to obtain 108.8 g of the modified epoxy resin.

实施例9Example 9

其制备方法具体包括：The preparation method specifically includes:

(3)取步骤(2)制备的膨胀的羟基化六方氮化硼(P-hBN-OH)25g，环己烷250mL装入1000mL带有搅拌器、回流分水器的三口烧瓶中，加热至回流，***内的水分由回流的溶剂逐步脱除，待回流分水器中没有水蒸出，降温至80℃，加入上述制备的式(Ⅰa)所示化合物237g，并将反应器放入超声波清洗器中，控制水温在70℃左右，超声搅拌反应24h，然后加入顺丁烯二酸酐4.5g、乙酸乙酯50mL，通入氮气，加热升温至100℃左右，回流反应4h，降温至65℃，减压抽滤，滤饼用甲苯/丙酮(1:1体积比)混合液清洗两次，然后再过滤，加入到500mL的甲苯/异丙醇混合液中形成微纳米分散液，以8000r/min的转速离心处理，取上层悬浮液，过滤、烘干(140℃)得所述含有乙烯基的疏水型六方氮化硼纳米片M-BNNSs(式(Ⅳ-4))14.8g，收率为59.1％；(3) Take 25 g of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in step (2), and put 250 mL of cyclohexane into a 1000 mL three-necked flask with a stirrer and reflux trap, and heat to Reflux, the water in the system is gradually removed by the refluxing solvent. When there is no water in the reflux separator, the temperature is reduced to 80°C, and 237g of the compound represented by formula (Ia) prepared above is added, and the reactor is placed in ultrasonic In the washer, control the water temperature at about 70°C, ultrasonically stir the reaction for 24h, then add 4.5g of maleic anhydride and 50mL of ethyl acetate, pour in nitrogen, heat to about 100°C, reflux for 4h, and cool down to 65°C , Vacuum filtration, the filter cake was washed twice with toluene/acetone (1:1 volume ratio) mixture, and then filtered, added to 500mL toluene/isopropanol mixture to form a micro-nano dispersion, at 8000r/ After centrifugation at a rotation speed of 1 min, the upper suspension was filtered and dried (140°C) to obtain the vinyl-containing hydrophobic hexagonal boron nitride nanosheets M-BNNSs (formula (IV-4)) 14.8 g, yield Is 59.1%;

式(Ⅳ-4)的结构式示意如下，仅显示了氮化硼纳米片上的一个羟基与顺丁烯二酸酐反应后共价连接的示意结构，在氮化硼纳米片上的其它羟基也可以与顺丁烯二酸酐反应后共价连接：The structural formula of formula (IV-4) is as follows. It only shows the schematic structure of a hydroxyl group on the boron nitride nanosheet reacted with maleic anhydride and covalently connected. The other hydroxyl groups on the boron nitride nanosheet can also be connected with the cis Covalent connection after reaction of butenedioic anhydride:

(b)改性环氧树脂的制备：(b) Preparation of modified epoxy resin:

(b-1)将环氧树脂E-44与正丁醇及1/4的BPO混合均匀，置于接有冷凝水管、氮气的四口烧瓶内，加入上述制备的式(Ⅳ-4)所示的含有乙烯基的疏水型六方氮化硼纳米片(M-BNNSs)，油浴加热到90℃恒温30min；(b-1) Mix epoxy resin E-44, n-butanol and 1/4 of BPO uniformly, place them in a four-necked flask connected with a condensed water pipe and nitrogen, and add the formula (IV-4) prepared above Hydrophobic hexagonal boron nitride nanosheets (M-BNNSs) containing vinyl as shown, heated in an oil bath to 90°C for 30 minutes;

(b-2)升温到110℃左右，并同时用恒压滴液漏斗滴加溶解有3/4BPO引发剂的混合单体(MAA及BA)溶液，缓慢滴加3 0min左右，滴完后保温反应3-4h，然后减压蒸馏除去正丁醇(可循环使用)即得所述改性环氧树脂(式Ⅴ-4)113.9g，合成路线示意如下：(b-2) The temperature is raised to about 110℃, and at the same time, the mixed monomer (MAA and BA) solution with 3/4BPO initiator dissolved in a constant pressure dropping funnel is added dropwise, and the solution is slowly added dropwise for about 3 0min, and the temperature is kept after dripping. After reacting for 3-4 hours, then distilling under reduced pressure to remove n-butanol (recyclable) to obtain 113.9 g of the modified epoxy resin (Formula V-4). The synthetic route is shown as follows:

x、y、z独立地为1～25之间的数，n为选自0-10的整数。x, y, and z are independently numbers between 1-25, and n is an integer selected from 0-10.

实施例10Example 10

其制备方法具体包括：The preparation method specifically includes:

(3)取步骤(2)制备的膨胀的羟基化六方氮化硼(P-hBN-OH)25g，环己烷250mL装入1000mL带有搅拌器、回流分水器的三口烧瓶中，加热至回流，***内的水分由回流的溶剂逐步脱除，待回流分水器中没有水蒸出，降温至80℃，加入上述制备的式(Ⅰb)所示化合物218g，并将反应器放入超声波清洗器中，控制水温在70℃左右，超声搅拌反应24h，然后加入顺丁烯二酸酐4.5g、乙酸乙酯50mL，通入氮气，加热升温至100℃左右，回流反应4h，降温至65℃，减压抽滤，滤饼用甲苯/丙酮(1:1体积比)混合液清洗两次，然后再过滤，加入到500mL的甲苯/异丙醇混合液中形成微纳米分散液，以8000r/min的转速离心处理，取上层悬浮液，过滤、烘干(140℃)得所述含有乙烯基的疏水型六方氮化硼纳米片M-BNNSs(式(Ⅳ-4))14.7g，收率为58.7％；(3) Take 25 g of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in step (2), and put 250 mL of cyclohexane into a 1000 mL three-necked flask with a stirrer and reflux trap, and heat to Reflux, the water in the system is gradually removed by the refluxing solvent. When there is no water in the reflux separator, the temperature is lowered to 80°C, 218g of the compound represented by formula (Ib) prepared above is added, and the reactor is placed in ultrasonic In the washer, control the water temperature at about 70°C, ultrasonically stir the reaction for 24h, then add 4.5g of maleic anhydride and 50mL of ethyl acetate, pour in nitrogen, heat to about 100°C, reflux for 4h, and cool down to 65°C , Vacuum filtration, the filter cake was washed twice with toluene/acetone (1:1 volume ratio) mixture, and then filtered, added to 500mL toluene/isopropanol mixture to form a micro-nano dispersion, at 8000r/ After centrifugation at a rotation speed of 1 min, the upper suspension was filtered and dried (140°C) to obtain the vinyl-containing hydrophobic hexagonal boron nitride nanosheets M-BNNSs (formula (IV-4)) 14.7 g, yield 58.7%;

(b)改性环氧树脂的制备：(b) Preparation of modified epoxy resin:

(b-1)将环氧树脂(E-44)与正丁醇及1/4的BPO混合均匀，置于接有冷凝水管、氮气的四口烧瓶内，加入上述制备的式(Ⅳ-4)所示的含有乙烯基的疏水型六方氮化硼纳米片(M-BNNSs)，油浴加热到90℃恒温30min；(b-1) Mix epoxy resin (E-44), n-butanol and 1/4 of BPO uniformly, place them in a four-necked flask connected with a condensed water pipe and nitrogen, and add the formula (Ⅳ-4) prepared above ) Shows the hydrophobic hexagonal boron nitride nanosheets (M-BNNSs) containing vinyl, heated in an oil bath to 90°C for 30 minutes;

(b-2)升温到110℃左右，并同时用恒压滴液漏斗滴加溶解有3/4BPO引发剂的混合单体(MAA及BA)溶液，缓慢滴加3 0min左右，滴完后保温反应3-4h，然后减压蒸馏除去正丁醇(可循环使用)即得所述改性环氧树脂113.8g。(b-2) The temperature is raised to about 110℃, and at the same time, the mixed monomer (MAA and BA) solution with 3/4BPO initiator dissolved in a constant pressure dropping funnel is added dropwise, and the solution is slowly added dropwise for about 3 0min, and the temperature is kept after dripping. After reacting for 3-4 hours, and then distilling under reduced pressure to remove the n-butanol (which can be recycled), 113.8 g of the modified epoxy resin is obtained.

对比例1Comparative example 1

本例提供一种改性环氧树脂，其原料包括：环氧树脂E-44 85g、疏水型六方氮化硼纳米片(M-BNNSs)6g、甲基丙烯酸甲酯(MAA)13g、丙烯酸丁酯(BA)7g。制备过程中所采用的溶剂为第三溶剂-正丁醇25g，引发剂为过氧化二苯甲酰(BPO)4g。This example provides a modified epoxy resin. Its raw materials include: epoxy resin E-44 85g, hydrophobic hexagonal boron nitride nanosheets (M-BNNSs) 6g, methyl methacrylate (MAA) 13g, butyl acrylate Ester (BA) 7g. The solvent used in the preparation process was 25 g of n-butanol, the third solvent, and 4 g of dibenzoyl peroxide (BPO) was the initiator.

其通过如下方法制备而得：It is prepared by the following method:

(一)制备疏水型六方氮化硼纳米片：(1) Preparation of hydrophobic hexagonal boron nitride nanosheets:

(1)制备羟基化六方氮化硼，具体实施方式为：将50g六方氮化硼(hBN纯度≥99％，粒径2～5μm)加入到1000ml的三口反应瓶中，然后加入事先配制好的5mol/L的氢氧化钠水溶液中，于100℃左右油浴加热条件下机械搅拌10h，所得的混合物经多次用蒸馏水洗涤至滤液为中性，烘干后得到羟基化六方氮化硼(hBN-OH)49.5g；(1) Preparation of hydroxylated hexagonal boron nitride, the specific implementation is: add 50g hexagonal boron nitride (hBN purity ≥99%, particle size 2-5μm) into a 1000ml three-necked reaction flask, and then add the pre-prepared In a 5mol/L sodium hydroxide aqueous solution, mechanically stirred for 10 hours under oil bath heating at about 100°C. The resulting mixture was washed with distilled water several times until the filtrate became neutral. After drying, hydroxylated hexagonal boron nitride (hBN -OH) 49.5g;

(2)制备膨胀的羟基化六方氮化硼，具体实施方式为：将步骤(1)中制备的羟基化六方氮化硼(hBN-OH)产物配制成质量分数为10％的蒸馏水溶液，放入-25℃左右的冰柜中冷冻处理5h，再解冻至室温，如此冻融循环6次，得到膨胀的羟基化六方氮化硼(P-hBN-OH)49.1g，经测定其表面羟基数为0.0209mmol/g；(2) Preparation of expanded hydroxylated hexagonal boron nitride, the specific implementation is: the hydroxylated hexagonal boron nitride (hBN-OH) product prepared in step (1) is formulated into a distilled aqueous solution with a mass fraction of 10%, and put Put it in a freezer at about -25°C for 5h, then thaw to room temperature, and then freeze-thaw cycles for 6 times to obtain 49.1g of expanded hydroxylated hexagonal boron nitride (P-hBN-OH). The number of hydroxyl groups on the surface is determined to be 0.0209mmol/g;

(3)取(2)制备的膨胀的羟基化六方氮化硼(P-hBN-OH)25g，加入混合溶剂(甲苯/环己烷＝1:1)250mL装入1000mL带有搅拌器的三口烧瓶中，加热至回流，***内的水分由回流的溶剂逐步脱除，待回流分水器中没有水蒸出，降温至80℃，加入聚乙二醇

86g，并将反应器放入超声波清洗器中，控制水温在70℃左右，超声搅拌反应24h，然后降温至65℃，沉淀30min，减压抽去溶剂； (3) Take 25g of the expanded hydroxylated hexagonal boron nitride (P-hBN-OH) prepared in (2), add 250mL of mixed solvent (toluene/cyclohexane=1:1) into 1000mL three ports with agitator In the flask, heat to reflux, and the water in the system is gradually removed by the refluxing solvent. When there is no water in the reflux trap, the temperature is reduced to 80°C, and polyethylene glycol is added.

86g, and put the reactor in an ultrasonic cleaner, control the water temperature at about 70°C, ultrasonically stir the reaction for 24h, then lower the temperature to 65°C, precipitate for 30min, and extract the solvent under reduced pressure;

(4)然后在获得的沉淀中加入亚油酸12g、加入混合溶剂(甲苯/环己烷＝1:1)100mL，通入氮气，加热升温至120℃左右，回流反应8h，降温至65℃，减压抽滤，滤饼用甲苯/丙酮(1:1体积比)混合液清洗两次，然后再过滤，加入到500mL的甲苯/异丙醇混合液中形成微纳米分散液，以8000r/min的转速离心处理，取上层悬浮液，过滤、烘干(140℃)得疏水型六方氮化硼纳米片(M-BNNSs)9.0g，收率为35.8％；(4) Then add 12g of linoleic acid to the obtained precipitate, add 100mL of mixed solvent (toluene/cyclohexane=1:1), pour in nitrogen, heat up to about 120℃, reflux for 8h, and cool to 65℃ , Vacuum filtration, the filter cake was washed twice with toluene/acetone (1:1 volume ratio) mixture, and then filtered, added to 500mL toluene/isopropanol mixture to form a micro-nano dispersion, at 8000r/ After centrifugation at a speed of 1 min, the upper suspension was filtered and dried (140°C) to obtain 9.0 g of hydrophobic hexagonal boron nitride nanosheets (M-BNNSs) with a yield of 35.8%;

(二)制备改性环氧树脂：(2) Preparation of modified epoxy resin:

(1)将环氧树脂E-44与正丁醇及1/4的BPO混合均匀，置于接有冷凝水管、氮气的四口烧瓶内，加入上述制备的疏水型六方氮化硼纳米片，油浴加热到90℃恒温30min；(1) Mix the epoxy resin E-44 with n-butanol and 1/4 of the BPO uniformly, place them in a four-necked flask connected with a condensate pipe and nitrogen, and add the hydrophobic hexagonal boron nitride nanosheets prepared above. Heat the oil bath to 90℃ for 30min;

(2)升温到110℃左右，并同时用恒压滴液漏斗滴加溶解有3/4BPO引发剂的混合单体(MAA及BA)溶液，缓慢滴加3 0min左右，滴完后保温反应3-4h，然后减压蒸馏除去正丁醇(可循环使用)即得改性环氧树脂113.6g。(2) The temperature is raised to about 110℃, and at the same time, the mixed monomer (MAA and BA) solution with 3/4BPO initiator dissolved in a constant pressure dropping funnel is added dropwise, and slowly dripped for about 3 0min. After the dripping is completed, the reaction is kept warm and 3 -4h, and then distill under reduced pressure to remove the n-butanol (recyclable) to obtain 113.6g of modified epoxy resin.

对比例1与本申请的差别在于未采用本申请的式(Ⅰ)所示的化合物进行剥离和酯化，导致需要两步进行反应且合成时间加倍。所得的疏水型六方氮化硼纳米片产物中含有未改性的六方氮化硼纳米片，且不易分离。因此，制备的改性环氧树脂中含有独立存在的未改性的六方氮化硼纳米片，影响产品的性能。The difference between Comparative Example 1 and the present application is that the compound represented by the formula (I) of the present application is not used for exfoliation and esterification, resulting in the need for two-step reaction and double the synthesis time. The obtained hydrophobic hexagonal boron nitride nanosheet product contains unmodified hexagonal boron nitride nanosheets and is not easy to separate. Therefore, the prepared modified epoxy resin contains unmodified hexagonal boron nitride nanosheets that exist independently, which affects the performance of the product.

对比例2Comparative example 2

直接用市售的六方氮化硼纳米片，其中，改性环氧树脂的原料包括：环氧树脂E-44 85g、市售的六方氮化硼纳米片(M-BNNSs)6g、甲基丙烯酸甲酯(MAA)13g、丙烯酸丁酯(BA)7g。制备过程中所采用的溶剂为第三溶剂-正丁醇25g，引发剂为过氧化二苯甲酰(BPO)4g。Directly use commercially available hexagonal boron nitride nanosheets. The raw materials of modified epoxy resin include: epoxy resin E-44 85g, commercially available hexagonal boron nitride nanosheets (M-BNNSs) 6g, methacrylic acid Methyl ester (MAA) 13g, butyl acrylate (BA) 7g. The solvent used in the preparation process was 25 g of n-butanol, the third solvent, and 4 g of dibenzoyl peroxide (BPO) was the initiator.

其制备方法具体包括：The preparation method specifically includes:

(1)将环氧树脂E-44与正丁醇及1/4的BPO混合均匀，置于接有冷凝水管、氮气的四口烧瓶内，加入市售的六方氮化硼纳米片(M-BNNSs)，油浴加热到90℃恒温30min；(1) Mix epoxy resin E-44, n-butanol and 1/4 of BPO uniformly, place them in a four-necked flask connected with a condensed water tube and nitrogen, and add commercially available hexagonal boron nitride nanosheets (M- BNNSs), the oil bath is heated to 90℃ for 30min;

(2)升温到110℃左右，并同时用恒压滴液漏斗滴加溶解有3/4BPO引发剂的混合单体(MAA及BA)溶液，缓慢滴加3 0min左右，滴完后保温反应3-4h，然后减压蒸馏除去正丁醇(可循环使用)即得改性环氧树脂113.8g。(2) The temperature is raised to about 110℃, and at the same time, the mixed monomer (MAA and BA) solution with 3/4BPO initiator dissolved in a constant pressure dropping funnel is added dropwise, and slowly dripped for about 3 0min. After the dripping is completed, the reaction is kept warm and 3 -4h, then vacuum distillation to remove the n-butanol (recyclable) to obtain 113.8g of modified epoxy resin.

对比例2与本申请的差别在于直接用市售的氮化硼纳米片，掺杂到丙烯酸酯类接枝环氧树脂体系中，虽可改善环氧树脂的脆性，抗冲击强度有所提高，但由于未改性的氮化硼纳米片与环氧树脂的相容性差，因而，导热率及固化物的电性能远远低于本申请。The difference between Comparative Example 2 and this application is that the commercially available boron nitride nanosheets are directly doped into the acrylic grafted epoxy resin system. Although the brittleness of the epoxy resin can be improved, the impact strength is improved. However, due to the poor compatibility of the unmodified boron nitride nanosheets with epoxy resin, the thermal conductivity and the electrical properties of the cured product are far lower than the application.

性能测试Performance Testing

将上述实施例3-10以及对比例1-2所得改性环氧树脂进行如下性能测试，具体参见表1。The modified epoxy resins obtained in the foregoing Examples 3-10 and Comparative Examples 1-2 were subjected to the following performance tests. See Table 1 for details.

表1Table 1

上述实施例只为说明本申请的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本申请的内容并据以实施，并不能以此限制本申请的保护范围，凡根据本申请精神实质所作的等效变化或修饰，都应涵盖在本申请的保护范围之内。The above embodiments are only to illustrate the technical ideas and features of this application, and their purpose is to enable those familiar with this technology to understand the content of this application and implement it accordingly, and cannot limit the scope of protection of this application. Equivalent changes or modifications made to the spirit and substance shall be covered by the scope of protection of this application.

Claims

一种改性环氧树脂，所述改性环氧树脂的原料包括环氧树脂，其特征在于，所述原料还包括含有酯基的乙烯基单体、含有乙烯基的疏水型六方氮化硼纳米片，所述改性环氧树脂由所述环氧树脂与剩余原料发生聚合反应制成；其中，所述含有乙烯基的疏水型六方氮化硼纳米片通过如下方法制备而得：A modified epoxy resin, the raw material of the modified epoxy resin includes epoxy resin, characterized in that the raw material further includes a vinyl monomer containing an ester group, and a hydrophobic hexagonal boron nitride containing a vinyl group Nanosheets, the modified epoxy resin is made by the polymerization reaction of the epoxy resin and the remaining raw materials; wherein the hydrophobic hexagonal boron nitride nanosheets containing vinyl are prepared by the following method:

(1)将六方氮化硼进行表面羟基化改性制备羟基化六方氮化硼；(1) Surface hydroxylation modification of hexagonal boron nitride to prepare hydroxylated hexagonal boron nitride;

(2)将步骤(1)制备的羟基化六方氮化硼进行冻融膨胀处理制备膨胀的羟基化六方氮化硼；(2) subjecting the hydroxylated hexagonal boron nitride prepared in step (1) to freeze-thaw expansion treatment to prepare expanded hydroxylated hexagonal boron nitride;

(3)将步骤(2)制备的膨胀的羟基化六方氮化硼与式(Ⅰ)所示的化合物在第一溶剂中混合搅拌，得第一混合溶液，然后向所得的第一混合溶液中加入不饱和酸和/或不饱和酸酐、第二溶剂，反应，制成所述含有乙烯基的疏水型六方氮化硼纳米片；(3) The expanded hydroxylated hexagonal boron nitride prepared in step (2) and the compound represented by formula (I) are mixed and stirred in the first solvent to obtain a first mixed solution, and then added to the obtained first mixed solution Adding unsaturated acid and/or unsaturated acid anhydride and a second solvent to react to prepare the hydrophobic hexagonal boron nitride nanosheets containing vinyl groups;

其中，R0为C1-6的烷基。
Wherein, R0 is a C1-6 alkyl group.
根据权利要求1所述的改性环氧树脂，其特征在于，所述含有酯基的乙烯基单体为选自式(Ⅱ)所示的化合物中的一种或多种的组合：The modified epoxy resin according to claim 1, wherein the vinyl monomer containing an ester group is one or a combination of one or more selected from the compounds represented by formula (II):

式中，R1为C1-10的烷基，R2、R3分别独立地为氢或C1-10的烷基。
In the formula, R1 is a C1-10 alkyl group, and R2 and R3 are each independently hydrogen or a C1-10 alkyl group.
根据权利要求2所述的改性环氧树脂，其特征在于，所述含有酯基的乙烯基单体为选自式(Ⅱ)所示的化合物中的至少两种。The modified epoxy resin according to claim 2, wherein the vinyl monomer containing an ester group is at least two selected from the group of compounds represented by formula (II).
根据权利要求1所述的改性环氧树脂，其特征在于，所述环氧树脂为双酚型环氧树脂。The modified epoxy resin of claim 1, wherein the epoxy resin is a bisphenol epoxy resin.
根据权利要求1或4所述的改性环氧树脂，其特征在于，所述环氧树脂为选自式(Ⅲ)所示的化合物中的一种或多种的组合：The modified epoxy resin according to claim 1 or 4, wherein the epoxy resin is a combination of one or more selected from the compounds represented by formula (III):

(Ⅲ)，式中：R4为-C(CH3)2-、-CH2-或-S(O)2-，n为选自0-10的整数。(III), where: R4 is -C(CH3)2-, -CH2- or -S(O)2-, and n is an integer selected from 0-10.
根据权利要求1所述的改性环氧树脂，其特征在于，所述环氧树脂、所述含有乙烯基的疏水型六方氮化硼纳米片和所述含有酯基的乙烯基单体的投料质量比为1∶0.05-0.1∶0.15-0.4；和/或，使所述聚合反应在温度100-120℃下进行。The modified epoxy resin of claim 1, wherein the epoxy resin, the vinyl-containing hydrophobic hexagonal boron nitride nanosheets, and the ester group-containing vinyl monomer are charged The mass ratio is 1:0.05-0.1:0.15-0.4; and/or, the polymerization reaction is carried out at a temperature of 100-120°C.
根据权利要求1所述的改性环氧树脂，其特征在于，步骤(1)中，所述羟基化六方氮化硼通过如下方法制备：将六方氮化硼与氢氧化钠水溶液混合，在温度90～150℃下搅拌反应，制成；和/或，步骤(2)中，所述冻融膨胀处理的操作方式为：将步骤(1)制备的羟基化六方氮化硼配制成水溶液，将所得水溶液在第一设定温度下冷冻，然后解冻至第二设定温度，如此循环冷冻、解冻步骤多次，制成所述膨胀的羟基化六方氮化硼；其中，所述第一设定温度为-50～-5℃，所述第二设定温度为10-30℃。The modified epoxy resin according to claim 1, characterized in that, in step (1), the hydroxylated hexagonal boron nitride is prepared by the following method: mixing hexagonal boron nitride and sodium hydroxide aqueous solution at a temperature Stirring and reacting at 90-150°C to prepare; and/or, in step (2), the operation of the freeze-thaw swelling treatment is: preparing the hydroxylated hexagonal boron nitride prepared in step (1) into an aqueous solution, and The resulting aqueous solution is frozen at a first set temperature, and then thawed to a second set temperature, so that the freezing and thawing steps are repeated multiple times to produce the expanded hydroxylated hexagonal boron nitride; wherein, the first set The temperature is -50 to -5°C, and the second set temperature is 10-30°C.
根据权利要求1所述的改性环氧树脂，其特征在于，步骤(3)中，所述混合搅拌在温度为60～78℃下进行；和/或，步骤(3)中，在所述第二溶剂中发生的所述反应在温度为80～120℃、惰性气体存在下进行；和/或，步骤(3)中，控制所述混合搅拌在无水环境中进行。The modified epoxy resin according to claim 1, wherein in step (3), the mixing and stirring are performed at a temperature of 60-78°C; and/or, in step (3), in the The reaction in the second solvent is carried out at a temperature of 80-120° C. in the presence of an inert gas; and/or, in step (3), the mixing and stirring are controlled to be carried out in an anhydrous environment.
根据权利要求1所述的改性环氧树脂，其特征在于，步骤(3)中，所述式(Ⅰ)所示的化合物与所述膨胀的羟基化六方氮化硼的投料质量比为6～12∶1，所述不饱和酸和/或不饱和酸酐与所述膨胀的羟基化六方氮化硼的投料质量比0.05～0.5∶1；和/或，步骤(3)中，所述第一溶剂为环己烷，所述第二溶剂为乙酸乙酯，所述不饱和酸为亚油酸和/或甲基丙烯酸，所述不饱和酸酐为衣康酸酐和/或顺丁烯二酸酐。The modified epoxy resin according to claim 1, wherein in step (3), the mass ratio of the compound represented by formula (I) to the expanded hydroxylated hexagonal boron nitride is 6 ~12:1, the feed mass ratio of the unsaturated acid and/or unsaturated acid anhydride to the expanded hydroxylated hexagonal boron nitride is 0.05~0.5:1; and/or, in step (3), the first The first solvent is cyclohexane, the second solvent is ethyl acetate, the unsaturated acid is linoleic acid and/or methacrylic acid, and the unsaturated acid anhydride is itaconic anhydride and/or maleic anhydride .
一种权利要求1-9中任一项权利要求所述的改性环氧树脂的制备方法，其特征在于，所述制备方法包括如下步骤：A method for preparing the modified epoxy resin according to any one of claims 1-9, wherein the method for preparing includes the following steps:

(a)制备含有乙烯基的疏水型六方氮化硼纳米片；(a) Preparation of hydrophobic hexagonal boron nitride nanosheets containing vinyl groups;

(b)使环氧树脂、步骤(a)制备的含有乙烯基的疏水型六方氮化硼纳米片以及剩余原料在引发剂存在下、在第三溶剂中发生聚合反应，生成所述改性环氧树脂。(b) The epoxy resin, the vinyl-containing hydrophobic hexagonal boron nitride nanosheets prepared in step (a), and the remaining raw materials are polymerized in the presence of an initiator in a third solvent to form the modified ring Oxy resin.