CN111777728B - A kind of preparation method of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material - Google Patents

A kind of preparation method of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material Download PDF

Info

Publication number
CN111777728B
CN111777728B CN202010663447.2A CN202010663447A CN111777728B CN 111777728 B CN111777728 B CN 111777728B CN 202010663447 A CN202010663447 A CN 202010663447A CN 111777728 B CN111777728 B CN 111777728B
Authority
CN
China
Prior art keywords
solution
graphene oxide
composite material
polymethyl methacrylate
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010663447.2A
Other languages
Chinese (zh)
Other versions
CN111777728A (en
Inventor
费杰
胡舒航
朱雅琼
王怡婷
周曼
刘振婷
谷岳峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN202010663447.2A priority Critical patent/CN111777728B/en
Publication of CN111777728A publication Critical patent/CN111777728A/en
Application granted granted Critical
Publication of CN111777728B publication Critical patent/CN111777728B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/44Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • C08K3/042Graphene or derivatives, e.g. graphene oxides

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a preparation method of a graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material, which comprises the following steps of carrying out hydrothermal reaction by taking a glucose solution as a carbon source to obtain carbon microspheres; dissolving carbon microspheres in a mixed solution of deionized water and absolute ethyl alcohol, adding a mixed solution of a silane coupling agent and absolute ethyl alcohol, and reacting under the heating condition of condensation reflux to obtain modified carbon microspheres; preparing a solution from the modified carbon microspheres, water and methyl methacrylate, recording the solution as a solution A, introducing nitrogen and continuously stirring; preparing a graphene oxide aqueous solution, marking as a solution B, and continuously stirring; adding the uniformly stirred solution B into the uniformly stirred solution A to obtain a solution C, and continuously stirring until the solution C is uniformly mixed; and adding sodium dodecyl benzene sulfonate into the solution C, heating for reaction, filtering, centrifuging, washing and drying a product to obtain the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material.

Description

一种氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料的 制备方法A kind of preparation method of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material

技术领域technical field

本发明属于纳米材料领域,具体涉及一种氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料的制备方法。The invention belongs to the field of nanomaterials, and in particular relates to a preparation method of a graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material.

背景技术Background technique

随着纳米科技的迅速发展,纳米材料润滑添加剂的研究开发及应用已成为国内外研究的热点之一。其中有机无机纳米复合材料的组装以及相关的纳米技术在制备新型纳米复合材料中越来越受到研究者的关注。这是由于纳米无机物与聚合物基体之间的协同作用,使得聚合物/无机纳米复合材料具有许多新奇的特性,比如优越的力学性能,热性能及稳定性,在高性能润滑油领域表现出了极大的应用价值。通过聚合物单体与无机颗粒表面的化学基团发生作用而使聚合物以化学键的形式包覆在粒子表面,不但可以加强聚合物单体与颗粒之间的作用力,而且复合粒子还可以根据实际需求选择不同的聚合物,使其在不同溶液中稳定存在。然而,纯的聚合物外壳通常由单一的化学交联而构成,使得其在高温下容易发生内部的软化,从而影响性能的发挥。With the rapid development of nanotechnology, the research, development and application of nanomaterial lubricating additives has become one of the hotspots of research at home and abroad. Among them, the assembly of organic-inorganic nanocomposites and related nanotechnology have attracted more and more attention of researchers in the preparation of new nanocomposites. This is due to the synergistic effect between the nano-inorganic matter and the polymer matrix, which makes the polymer/inorganic nanocomposite have many novel properties, such as superior mechanical properties, thermal properties and stability, which are shown in the field of high-performance lubricants. great application value. Through the interaction between the polymer monomer and the chemical groups on the surface of the inorganic particles, the polymer is coated on the surface of the particle in the form of chemical bonds, which can not only strengthen the force between the polymer monomer and the particle, but also can enhance the interaction between the polymer monomer and the particle. According to practical requirements, different polymers are selected to be stable in different solutions. However, the pure polymer shell is usually composed of a single chemical crosslink, which makes it prone to internal softening at high temperature, which affects the performance.

发明内容SUMMARY OF THE INVENTION

本发明的目的在于提供一种氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料的制备方法,以克服现有技术存在的缺陷,本发明在不加入引发剂和交联剂的条件下制备出氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料,制备过程简单且无有害物质产生;此外,本发明所制备的高性能纳米复合材料能够在摩擦过程中降低机械的摩擦系数和磨损率,进而延长机械使用寿命,且成本低,具有一定的商用前景。The object of the present invention is to provide a kind of preparation method of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material, to overcome the defects existing in the prior art, the present invention does not add initiator and crosslinking agent condition The graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material is prepared under the following conditions, and the preparation process is simple and no harmful substances are generated; in addition, the high-performance nano-composite material prepared by the present invention can reduce the mechanical friction during the friction process. coefficient and wear rate, thereby prolonging the service life of machinery, and low cost, which has certain commercial prospects.

为达到上述目的,本发明采用如下技术方案:To achieve the above object, the present invention adopts the following technical solutions:

一种氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料的制备方法,包括以下步骤:A preparation method of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material, comprising the following steps:

1)以葡萄糖溶液为碳源进行水热反应,反应结束后将产物洗涤若干次,然后抽滤、干燥后得到碳微球;1) carry out hydrothermal reaction with glucose solution as carbon source, after the reaction finishes, the product is washed several times, then suction filtration and drying are obtained to obtain carbon microspheres;

2)将干燥的碳微球溶于去离子水和无水乙醇的混合溶液中,加入硅烷偶联剂和无水乙醇的混合溶液,在冷凝回流加热条件下进行反应,反应结束后将产物洗涤若干次,然后抽滤、干燥后得到改性碳微球;2) Dissolve the dried carbon microspheres in a mixed solution of deionized water and absolute ethanol, add a mixed solution of silane coupling agent and absolute ethanol, react under the condition of condensation and reflux heating, and wash the product after the reaction is completed. Several times, then suction filtration and drying to obtain modified carbon microspheres;

3)将干燥后的改性碳微球、水和甲基丙烯酸甲酯配成溶液,记为溶液A,通入氮气并持续搅拌至混合均匀;3) The modified carbon microspheres after drying, water and methyl methacrylate are made into a solution, denoted as solution A, feed nitrogen and continue to stir until the mixture is uniform;

4)配制氧化石墨烯水溶液,记为溶液B,持续搅拌至混合均匀;4) prepare an aqueous solution of graphene oxide, denoted as solution B, and continue to stir until uniformly mixed;

5)将搅拌均匀的溶液B加入到搅拌混合均匀的溶液A中,得到溶液C,并持续搅拌至混合均匀;5) Add the well-stirred solution B to the well-stirred solution A to obtain the solution C, and continue to stir until the well-mixed solution;

6)将十二烷基苯磺酸钠加入到上述搅拌混合均匀的溶液C中并加热进行反应,整个过程持续通入氮气并搅拌;6) Sodium dodecylbenzene sulfonate is added in the above-mentioned stirred and mixed solution C and heated to react, and the whole process continues to be fed with nitrogen and stirred;

7)待反应结束,将产物过滤、离心、洗涤并干燥,即得到氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料。7) After the reaction is completed, the product is filtered, centrifuged, washed and dried to obtain the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material.

进一步地,步骤1)所述的葡萄糖溶液浓度为40mg/mL;步骤1)中水热反应的温度为180℃,时间为12h。Further, the concentration of the glucose solution in step 1) is 40 mg/mL; the temperature of the hydrothermal reaction in step 1) is 180° C. and the time is 12 h.

进一步地,步骤2)中去离子水和无水乙醇的混合溶液中去离子水和无水乙醇的体积比为5:4,且每90mL去离子水和无水乙醇的混合溶液中加入0.2g碳微球。Further, the volume ratio of deionized water and absolute ethanol in the mixed solution of deionized water and absolute ethanol in step 2) is 5:4, and 0.2g is added in the mixed solution of every 90 mL of deionized water and absolute ethanol. carbon microspheres.

进一步地,步骤2)中硅烷偶联剂采用KH550,硅烷偶联剂和无水乙醇的混合溶液具体为:每20mL无水乙醇中加入5mL硅烷偶联剂。Further, in step 2), KH550 is used as the silane coupling agent, and the mixed solution of the silane coupling agent and absolute ethanol is specifically: 5 mL of silane coupling agent is added to every 20 mL of absolute ethanol.

进一步地,步骤2)中去离子水和无水乙醇的混合溶液与硅烷偶联剂和无水乙醇的混合溶液的体积比为18:5。Further, in step 2), the volume ratio of the mixed solution of deionized water and absolute ethanol to the mixed solution of silane coupling agent and absolute ethanol is 18:5.

进一步地,步骤2)中冷凝回流加热条件具体为:在60℃下冷凝回流12h。Further, the condensation and reflux heating conditions in step 2) are specifically: condensation and reflux at 60° C. for 12 hours.

进一步地,步骤3)溶液A中改性碳微球的浓度为5mg/mL-8mg/mL,且甲基丙烯酸甲酯加入量为改性碳微球质量的0.2wt%。Further, in step 3) the concentration of the modified carbon microspheres in solution A is 5 mg/mL-8 mg/mL, and the amount of methyl methacrylate added is 0.2 wt % of the mass of the modified carbon microspheres.

进一步地,步骤5)溶液C中氧化石墨烯与改性碳微球的质量比为1:5。Further, the mass ratio of graphene oxide and modified carbon microspheres in step 5) solution C is 1:5.

进一步地,步骤5)中溶液A和溶液B之间的体积比为2:1。Further, the volume ratio between solution A and solution B in step 5) is 2:1.

进一步地,步骤6)中十二烷基苯磺酸钠加入质量与改性碳微球的质量比为1:40,步骤6)中反应温度为60℃,反应时间为12h。Further, in the step 6), the mass ratio of the sodium dodecylbenzene sulfonate added to the modified carbon microspheres is 1:40, the reaction temperature in the step 6) is 60°C, and the reaction time is 12h.

与现有技术相比,本发明具有以下有益的技术效果:Compared with the prior art, the present invention has the following beneficial technical effects:

本发明采用化学法改性碳微球,再配制改性碳微球和聚甲基丙烯酸甲酯(PMMA)的混合溶液。配制氧化石墨烯(GO)水溶液,搅拌均匀后加入到改性碳微球和PMMA的混合溶液中,加入十二烷基苯磺酸钠后在N2氛围下加热处理得到氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料。通过观察与分析,PMMA聚合物壳包覆在碳微球表面,GO在PMMA网络中作为物理交联点增强聚合物网络的机械性能。在摩擦过程中,小尺寸颗粒会稳定沉积到摩擦区域中,降低摩擦副表面的粗糙度,避免滑动表面之间的直接接触,一定程度上起到修复摩擦副表面的作用,同时,聚合物壳在摩擦过程中会促进润滑油膜的形成进而降低磨损。大尺寸的颗粒则充当了轴承,使得滑动摩擦装变为滚动摩擦,GO则有助于增强摩擦膜的强度,防止其破裂,提高摩擦稳定性。此方法充分发挥碳微球,PMMA和GO的协同作用,有效改善复合材料机械性能和分散性差的问题。大幅度降低摩擦系数和磨损率,提高了稳定性和机械的使用寿命。The invention adopts chemical method to modify carbon microspheres, and then prepares a mixed solution of modified carbon microspheres and polymethyl methacrylate (PMMA). Graphene oxide (GO) aqueous solution was prepared, stirred evenly, added to the mixed solution of modified carbon microspheres and PMMA, added with sodium dodecyl benzene sulfonate and heated under N atmosphere to obtain graphene oxide reinforced polymethyl methacrylate Methyl acrylate/carbon microsphere composites. Through observation and analysis, the PMMA polymer shell is coated on the surface of the carbon microspheres, and GO acts as a physical cross-linking point in the PMMA network to enhance the mechanical properties of the polymer network. During the friction process, the small-sized particles will be stably deposited in the friction area, reducing the roughness of the surface of the friction pair, avoiding direct contact between the sliding surfaces, and repairing the surface of the friction pair to a certain extent. At the same time, the polymer shell During the friction process, it promotes the formation of lubricating oil film and reduces wear. The large-sized particles act as bearings, turning the sliding friction device into rolling friction, and GO helps to strengthen the friction film, prevent it from cracking, and improve friction stability. This method gives full play to the synergistic effect of carbon microspheres, PMMA and GO to effectively improve the mechanical properties and poor dispersibility of composites. The friction coefficient and wear rate are greatly reduced, and the stability and the service life of the machine are improved.

本发明首次制备了氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料。首先采用硅烷偶联剂对碳微球进行改性处理,为接下来的与甲基丙烯酸甲酯(MMA)以及氧化石墨烯(GO)的复合提供了先决条件,同时通过接枝长的烷烃链,使得其在有机溶剂中具有良好的分散性,并且具有操作简单,对设备要求低等特点。其次MMA和碳微球通过酰胺键结合,并且在十二烷基苯磺酸钠的作用和加热条件下,引发MMA分子的双键打开并和氧化石墨烯(GO)纳米片发生反应,形成含氧化石墨烯的聚甲基丙烯酸甲酯外壳。由于PMMA的柔性分子链,使得复合材料在摩擦过程中表现得更稳定。而且,GO具有优异的机械性能,增强了PMMA的耐磨性和稳定性,同时提高了复合材料的导热性,对摩擦副表面起到了很好的保护作用,极大的降低了磨损率,有利于提高机械的使用寿命性能。使用水热碳球为原料,原材料来源广泛,更环保。整个制备过程不添加有毒物质,总的说是一种绿色且过程可控的制备方法。The present invention prepares the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material for the first time. First, the carbon microspheres were modified with a silane coupling agent, which provided a prerequisite for the subsequent compounding with methyl methacrylate (MMA) and graphene oxide (GO). At the same time, by grafting long alkane chains , so that it has good dispersibility in organic solvents, and has the characteristics of simple operation and low equipment requirements. Secondly, MMA and carbon microspheres are combined through amide bonds, and under the action of sodium dodecylbenzenesulfonate and heating conditions, the double bonds of MMA molecules are opened and reacted with graphene oxide (GO) nanosheets to form nanosheets containing Polymethyl methacrylate shell of graphene oxide. Due to the flexible molecular chain of PMMA, the composite material is more stable during friction. Moreover, GO has excellent mechanical properties, enhances the wear resistance and stability of PMMA, and at the same time improves the thermal conductivity of the composite material, which plays a good role in protecting the surface of the friction pair, greatly reducing the wear rate. Conducive to improving the service life of the machine. Using hydrothermal carbon balls as raw materials, the raw materials are widely sourced and more environmentally friendly. No toxic substances are added in the whole preparation process, and generally speaking, it is a green and process-controllable preparation method.

附图说明Description of drawings

图1为实施例1改性前后碳微球的SEM照片对比图,其中(a)为未改性的碳微球微观形貌,(b)为改性后碳微球的微观形貌,(c)和(d)为复合材料的微观形貌;Fig. 1 is a comparison diagram of SEM photos of carbon microspheres before and after modification in Example 1, wherein (a) is the microscopic morphology of the unmodified carbon microspheres, (b) is the microscopic morphology of the modified carbon microspheres, ( c) and (d) are the microstructures of the composites;

图2为碳微球,改性碳微球,氧化石墨烯和通过实施例1得到的氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料的拉曼图谱。2 is the Raman spectrum of carbon microspheres, modified carbon microspheres, graphene oxide and the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material obtained by Example 1.

图3为原始油、碳微球和通过实施例1得到的氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料的动摩擦系数图,其中(a)为在8N的动摩擦系数图,(b)为在30N下的动摩擦系数图;Fig. 3 is the kinetic friction coefficient diagram of original oil, carbon microspheres and the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material obtained by Example 1, wherein (a) is the kinetic friction coefficient diagram at 8N, ( b) is the dynamic friction coefficient diagram under 30N;

具体实施方式Detailed ways

下面对本发明的实施方式做进一步详细描述:Embodiments of the present invention are described in further detail below:

一种氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料的制备方法,包括以下步骤:A preparation method of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material, comprising the following steps:

1)以葡萄糖溶液为碳源,通过水热反应,水热反应的温度为180℃,时间为12h,结束后将产物洗涤多次,抽滤,干燥后得到碳微球,其中葡萄糖溶液浓度为40mg/mL;1) Using glucose solution as carbon source, through hydrothermal reaction, the temperature of hydrothermal reaction is 180 ° C, and the time is 12 h, after the end, the product is washed several times, suction filtered, and dried to obtain carbon microspheres, wherein the concentration of glucose solution is 40mg/mL;

2)将干燥的碳微球溶于水和无水乙醇的混合溶液(去离子水和无水乙醇的体积比为5:4)中,且每90mL去离子水和无水乙醇的混合溶液中加入0.2g碳微球,然后加入硅烷偶联剂和无水乙醇的混合溶液(硅烷偶联剂采用KH550,硅烷偶联剂和无水乙醇的混合溶液具体为:每20mL无水乙醇中加入5ml硅烷偶联剂),在在60℃下冷凝回流12h,将产物洗涤多次,抽滤,干燥后得到改性碳微球;2) Dissolve the dried carbon microspheres in a mixed solution of water and absolute ethanol (the volume ratio of deionized water and absolute ethanol is 5:4), and every 90 mL of the mixed solution of deionized water and absolute ethanol Add 0.2g of carbon microspheres, then add the mixed solution of silane coupling agent and absolute ethanol (KH550 is used for silane coupling agent, and the mixed solution of silane coupling agent and absolute ethanol is specifically: add 5ml per 20mL of absolute ethanol Silane coupling agent), condensed and refluxed at 60°C for 12h, washed the product several times, suction filtered, and dried to obtain modified carbon microspheres;

3)将干燥后的改性碳微球水和甲基丙烯酸甲酯配成溶液A,溶液A中改性碳微球的浓度为5mg/mL-8mg/mL,甲基丙烯酸甲酯的加入量为碳微球质量的0.2wt%,通入氮气并持续搅拌;3) The dried modified carbon microspheres water and methyl methacrylate are made into solution A, the concentration of the modified carbon microspheres in solution A is 5mg/mL-8mg/mL, and the amount of methyl methacrylate added It is 0.2wt% of the mass of carbon microspheres, nitrogen is introduced and stirring is continued;

4)配置氧化石墨烯水溶液,记为溶液B,氧化石墨烯与溶液A中改性碳微球的质量比为1:5。4) Configure an aqueous solution of graphene oxide, denoted as solution B, and the mass ratio of graphene oxide to modified carbon microspheres in solution A is 1:5.

5)将溶液B加入到溶液A中(A与B溶液体积比2:1)并加入十二烷基苯磺酸钠后升温至70℃,其中十二烷基苯磺酸钠加入质量为与改性碳微球的质量比为1:40。冷凝回流12小时,整个过程持续通入氮气并搅拌,将产物用乙醇反复洗涤,抽滤,干燥得到具有氧化石墨烯增强的聚甲基丙烯酸甲酯/碳微球复合材料。5) solution B is added in solution A (volume ratio of A and B solution is 2:1) and after adding sodium dodecyl benzene sulfonate, it is warming up to 70 ° C, wherein the added quality of sodium dodecyl benzene sulfonate is the same as that of sodium dodecyl benzene sulfonate. The mass ratio of modified carbon microspheres was 1:40. Condensed and refluxed for 12 hours, the whole process was continuously fed with nitrogen and stirred, the product was repeatedly washed with ethanol, suction filtered, and dried to obtain a graphene oxide-reinforced polymethyl methacrylate/carbon microsphere composite material.

本发明方法采用无皂聚合法,在不使用乳化剂和交联剂的条件下制备出的复合材料在有机溶剂中有很好的分散性和稳定性,并且具有可降解性,绿色无污染。作为润滑油添加剂分散到润滑油中,能有效降低摩擦系数,减少磨损率,有效延长设备的使用寿命,并且制备过程可控,可根据不同需求制备不同比例,不同尺寸的产物,为高性能纳米润滑剂的制备提供了多样性。本发明将氧化石墨烯加入到聚合物网络中作为物理交联位点,构建物理化学交联网络来增强聚合物的机械性能。The method of the invention adopts a soap-free polymerization method, and the composite material prepared without using an emulsifier and a cross-linking agent has good dispersibility and stability in an organic solvent, is degradable, and is green and pollution-free. Dispersing into the lubricating oil as a lubricant additive can effectively reduce the friction coefficient, reduce the wear rate, effectively prolong the service life of the equipment, and the preparation process is controllable, and products of different proportions and sizes can be prepared according to different needs, which is a high-performance nanometer. The preparation of lubricants offers variety. In the present invention, graphene oxide is added into the polymer network as a physical cross-linking site, and a physical-chemical cross-linking network is constructed to enhance the mechanical properties of the polymer.

实施例1Example 1

1)配置浓度为40mg/mL的葡萄糖溶液,在180℃进行热水热反应12h,将产物洗涤多次,抽滤,80℃烘箱中干燥12h后得到碳微球;1) Prepare a glucose solution with a concentration of 40 mg/mL, carry out a hot water thermal reaction at 180 °C for 12 hours, wash the product for several times, filter it with suction, and dry it in an oven at 80 °C for 12 hours to obtain carbon microspheres;

2)将干燥的0.2g碳微球溶于50ml去离子水和40ml无水乙醇的混合溶液中,加入5ml硅烷偶联剂和20ml无水乙醇配备的混合溶液,在60℃冷凝回流条件下反应12h,将产物洗涤多次,抽滤,80℃烘箱干燥12h后得到改性碳微球;2) Dissolve the dried 0.2g carbon microspheres in a mixed solution of 50ml of deionized water and 40ml of absolute ethanol, add a mixed solution of 5ml of silane coupling agent and 20ml of absolute ethanol, and react at 60°C under condensation and reflux conditions 12h, the product was washed several times, filtered with suction, and dried in an oven at 80°C for 12h to obtain modified carbon microspheres;

3)将干燥后的改性碳微球,水和甲基丙烯酸甲酯配成溶液A,其中溶液A中改性碳微球的浓度为5mg/mL,甲基丙烯酸甲酯的加入量为改性碳微球质量的0.2wt%,通入氮气并持续搅拌;3) The modified carbon microspheres after drying, water and methyl methacrylate are made into solution A, wherein the concentration of the modified carbon microspheres in the solution A is 5mg/mL, and the addition of methyl methacrylate is 5 mg/mL. 0.2wt% of the mass of the carbon microspheres, pass nitrogen and continue to stir;

4)配置氧化石墨烯水溶液,记为溶液B,氧化石墨烯与改性碳微球的质量比为1:5;4) configure an aqueous solution of graphene oxide, denoted as solution B, and the mass ratio of graphene oxide to modified carbon microspheres is 1:5;

5)将溶液B加入到溶液A中(A与B溶液体积比2:1)并加入十二烷基苯磺酸钠后升温至70℃,其中十二烷基苯磺酸钠加的量为与改性碳微球的质量比为1:40。冷凝回流12小时,整个过程持续通入氮气并搅拌,将产物用乙醇反复洗涤,抽滤,干燥得到具有氧化石墨烯增强的聚甲基丙烯酸甲酯/碳微球复合材料。5) adding solution B in solution A (volume ratio of A and B solution is 2:1) and be warming up to 70° C. after adding sodium dodecylbenzenesulfonate, wherein the amount that sodium dodecylbenzenesulfonate adds is The mass ratio to modified carbon microspheres is 1:40. Condensed and refluxed for 12 hours, the whole process was continuously fed with nitrogen and stirred, the product was repeatedly washed with ethanol, suction filtered, and dried to obtain a graphene oxide-reinforced polymethyl methacrylate/carbon microsphere composite material.

实施例2Example 2

1)配置浓度为40mg/mL的葡萄糖溶液,在180℃进行热水热反应12h,将产物洗涤多次,抽滤,80℃烘箱中干燥12h后得到碳微球;1) Prepare a glucose solution with a concentration of 40 mg/mL, carry out a hot water thermal reaction at 180 °C for 12 hours, wash the product for several times, filter it with suction, and dry it in an oven at 80 °C for 12 hours to obtain carbon microspheres;

2)将干燥的0.2g碳微球溶于50ml去离子水和40ml无水乙醇的混合溶液中,加入5ml硅烷偶联剂和20ml无水乙醇配备的混合溶液,在60℃冷凝回流条件下反应12h,将产物洗涤多次,抽滤,80℃烘箱干燥12h后得到改性碳微球;2) Dissolve the dried 0.2g carbon microspheres in a mixed solution of 50ml of deionized water and 40ml of absolute ethanol, add a mixed solution of 5ml of silane coupling agent and 20ml of absolute ethanol, and react at 60°C under condensation and reflux conditions 12h, the product was washed several times, filtered with suction, and dried in an oven at 80°C for 12h to obtain modified carbon microspheres;

3)将干燥后的改性碳微球,水和甲基丙烯酸甲酯配成溶液A,其中溶液A中改性碳微球的浓度为6mg/mL,甲基丙烯酸甲酯的加入量为改性碳微球质量的0.2wt%,通入氮气并持续搅拌;3) The modified carbon microspheres after drying, water and methyl methacrylate are made into solution A, wherein the concentration of the modified carbon microspheres in solution A is 6 mg/mL, and the addition of methyl methacrylate is changed to 0.2wt% of the mass of the carbon microspheres, pass nitrogen and continue to stir;

4)配置氧化石墨烯水溶液,记为溶液B,氧化石墨烯与改性碳微球的质量比为1:5;4) configure an aqueous solution of graphene oxide, denoted as solution B, and the mass ratio of graphene oxide to modified carbon microspheres is 1:5;

5)将溶液B加入到溶液A中(A与B溶液体积比2:1)并加入十二烷基苯磺酸钠后升温至70℃,其中十二烷基苯磺酸钠加的量为与改性碳微球的质量比为1:40。冷凝回流12小时,整个过程持续通入氮气并搅拌,将产物用乙醇反复洗涤,抽滤,干燥得到具有氧化石墨烯增强的聚甲基丙烯酸甲酯/碳微球复合材料。5) adding solution B in solution A (volume ratio of A and B solution is 2:1) and be warming up to 70° C. after adding sodium dodecylbenzenesulfonate, wherein the amount that sodium dodecylbenzenesulfonate adds is The mass ratio to modified carbon microspheres is 1:40. Condensed and refluxed for 12 hours, the whole process was continuously fed with nitrogen and stirred, the product was repeatedly washed with ethanol, suction filtered, and dried to obtain a graphene oxide-reinforced polymethyl methacrylate/carbon microsphere composite material.

实施例3Example 3

1)配置浓度为40mg/mL的葡萄糖溶液,在180℃进行热水热反应12h,将产物洗涤多次,抽滤,80℃烘箱中干燥12h后得到碳微球;1) Prepare a glucose solution with a concentration of 40 mg/mL, carry out a hot water thermal reaction at 180 °C for 12 hours, wash the product for several times, filter it with suction, and dry it in an oven at 80 °C for 12 hours to obtain carbon microspheres;

2)将干燥的0.2g碳微球溶于50ml去离子水和40ml无水乙醇的混合溶液中,加入5ml硅烷偶联剂和20ml无水乙醇配备的混合溶液,在60℃冷凝回流条件下反应12h,将产物洗涤多次,抽滤,80℃烘箱干燥12h后得到改性碳微球;2) Dissolve the dried 0.2g carbon microspheres in a mixed solution of 50ml of deionized water and 40ml of absolute ethanol, add a mixed solution of 5ml of silane coupling agent and 20ml of absolute ethanol, and react at 60°C under condensation and reflux conditions 12h, the product was washed several times, filtered with suction, and dried in an oven at 80°C for 12h to obtain modified carbon microspheres;

3)将干燥后的改性碳微球,水和甲基丙烯酸甲酯配成溶液A,其中溶液A中改性碳微球的浓度为7mg/mL,甲基丙烯酸甲酯的加入量为改性碳微球质量的0.2wt%,通入氮气并持续搅拌;3) The modified carbon microspheres after drying, water and methyl methacrylate are made into solution A, wherein the concentration of the modified carbon microspheres in solution A is 7 mg/mL, and the addition of methyl methacrylate is changed to 0.2wt% of the mass of the carbon microspheres, pass nitrogen and continue to stir;

4)配置氧化石墨烯水溶液,记为溶液B,氧化石墨烯与改性碳微球的质量比为1:5;4) configure an aqueous solution of graphene oxide, denoted as solution B, and the mass ratio of graphene oxide to modified carbon microspheres is 1:5;

5)将溶液B加入到溶液A中(A与B溶液体积比2:1)并加入十二烷基苯磺酸钠后升温至70℃,其中十二烷基苯磺酸钠加的量为与改性碳微球的质量比为1:40。冷凝回流12小时,整个过程持续通入氮气并搅拌,将产物用乙醇反复洗涤,抽滤,干燥得到具有氧化石墨烯增强的聚甲基丙烯酸甲酯/碳微球复合材料。5) adding solution B in solution A (volume ratio of A and B solution is 2:1) and be warming up to 70° C. after adding sodium dodecylbenzenesulfonate, wherein the amount that sodium dodecylbenzenesulfonate adds is The mass ratio to modified carbon microspheres is 1:40. Condensed and refluxed for 12 hours, the whole process was continuously fed with nitrogen and stirred, the product was repeatedly washed with ethanol, suction filtered, and dried to obtain a graphene oxide-reinforced polymethyl methacrylate/carbon microsphere composite material.

实施例4Example 4

1)配置浓度为50mg/mL的葡萄糖溶液,在180℃进行热水热反应12h,将产物洗涤多次,抽滤,80℃烘箱中干燥12h后得到碳微球;1) Prepare a glucose solution with a concentration of 50 mg/mL, carry out a hot water thermal reaction at 180 °C for 12 hours, wash the product for several times, filter it with suction, and dry it in an oven at 80 °C for 12 hours to obtain carbon microspheres;

2)将干燥的0.2g碳微球溶于50ml去离子水和40ml无水乙醇的混合溶液中,加入5ml硅烷偶联剂和20ml无水乙醇配备的混合溶液,在60℃冷凝回流条件下反应12h,将产物洗涤多次,抽滤,80℃烘箱干燥12h后得到改性碳微球;2) Dissolve the dried 0.2g carbon microspheres in a mixed solution of 50ml of deionized water and 40ml of absolute ethanol, add a mixed solution of 5ml of silane coupling agent and 20ml of absolute ethanol, and react at 60°C under condensation and reflux conditions 12h, the product was washed several times, filtered with suction, and dried in an oven at 80°C for 12h to obtain modified carbon microspheres;

3)将干燥后的改性碳微球,水和甲基丙烯酸甲酯配成溶液A,其中溶液A中改性碳微球的浓度为8mg/mL,甲基丙烯酸甲酯的加入量为改性碳微球质量的0.2wt%,通入氮气并持续搅拌;3) The modified carbon microspheres after drying, water and methyl methacrylate are made into solution A, wherein the concentration of the modified carbon microspheres in solution A is 8 mg/mL, and the addition of methyl methacrylate is changed to 0.2wt% of the mass of the carbon microspheres, pass nitrogen and continue to stir;

4)配置氧化石墨烯水溶液,记为溶液B,氧化石墨烯与改性碳微球的质量比为1:5;4) configure an aqueous solution of graphene oxide, denoted as solution B, and the mass ratio of graphene oxide to modified carbon microspheres is 1:5;

5)将溶液B加入到溶液A中(A与B溶液体积比2:1)并加入十二烷基苯磺酸钠后升温至70℃,其中十二烷基苯磺酸钠加的量为与改性碳微球的质量比为1:40。冷凝回流12小时,整个过程持续通入氮气并搅拌,将产物用乙醇反复洗涤,抽滤,干燥得到具有氧化石墨烯增强的聚甲基丙烯酸甲酯/碳微球复合材料。5) adding solution B in solution A (volume ratio of A and B solution is 2:1) and be warming up to 70° C. after adding sodium dodecylbenzenesulfonate, wherein the amount that sodium dodecylbenzenesulfonate adds is The mass ratio to modified carbon microspheres is 1:40. Condensed and refluxed for 12 hours, the whole process was continuously fed with nitrogen and stirred, the product was repeatedly washed with ethanol, suction filtered, and dried to obtain a graphene oxide-reinforced polymethyl methacrylate/carbon microsphere composite material.

从图1中对比通过实施例1得到的原始碳微球与硅烷偶联剂改性处理后的碳微球,可以看出本发明采用的改性方法成功的将硅烷偶联剂接枝到了碳微球表面;观察改性后的碳微球和氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料可知,本发明制备复合材料的方法,成功将碳微球,甲基丙烯酸甲酯和氧化石墨烯结合在了一起,氧化石墨烯引入到了聚甲基丙烯酸甲酯网络中。Comparing the original carbon microspheres obtained by Example 1 and the carbon microspheres modified by the silane coupling agent in FIG. 1, it can be seen that the modification method adopted in the present invention successfully grafts the silane coupling agent to the carbon microspheres. The surface of the microspheres; observing the modified carbon microspheres and graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite materials, it can be seen that the method for preparing the composite material of the present invention successfully combines the carbon microspheres, methyl methacrylate Combined with graphene oxide, graphene oxide is introduced into the polymethyl methacrylate network.

从图2中可以看到,Raman图谱中出现了氧化石墨烯的特征峰,说明氧化石墨烯存在于复合材料中。As can be seen from Figure 2, the characteristic peaks of graphene oxide appear in the Raman spectrum, indicating that graphene oxide exists in the composite material.

从图3中可以看出转速为400R不变,随着压力的变化,(a)8N(b)30N单独添加碳微球的润滑油和原始油对于压力的变化更为明显,本发明通过实施例1制备的复合材料加入到润滑油后摩擦系数更低,说明复合材料具有更好的减摩性能。It can be seen from Fig. 3 that the rotation speed is 400R unchanged. With the change of pressure, (a) 8N (b) 30N alone adding carbon microspheres to the lubricating oil and the original oil have more obvious changes in pressure. The friction coefficient of the composite material prepared in Example 1 is lower after being added to the lubricating oil, indicating that the composite material has better anti-friction performance.

Claims (10)

1.一种氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料的制备方法,其特征在于,包括以下步骤:1. a preparation method of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material, is characterized in that, may further comprise the steps: 1)以葡萄糖溶液为碳源进行水热反应,反应结束后将产物洗涤若干次,然后抽滤、干燥后得到碳微球;1) carry out hydrothermal reaction with glucose solution as carbon source, after the reaction finishes, the product is washed several times, then suction filtration and drying are obtained to obtain carbon microspheres; 2)将干燥的碳微球溶于去离子水和无水乙醇的混合溶液中,加入硅烷偶联剂和无水乙醇的混合溶液,在冷凝回流加热条件下进行反应,反应结束后将产物洗涤若干次,然后抽滤、干燥后得到改性碳微球;2) Dissolve the dried carbon microspheres in a mixed solution of deionized water and absolute ethanol, add a mixed solution of silane coupling agent and absolute ethanol, react under the condition of condensation and reflux heating, and wash the product after the reaction is completed. Several times, then suction filtration and drying to obtain modified carbon microspheres; 3)将干燥后的改性碳微球、水和甲基丙烯酸甲酯配成溶液,记为溶液A,通入氮气并持续搅拌至混合均匀;3) The modified carbon microspheres after drying, water and methyl methacrylate are made into a solution, denoted as solution A, feed nitrogen and continue to stir until the mixture is uniform; 4)配制氧化石墨烯水溶液,记为溶液B,持续搅拌至混合均匀;4) prepare an aqueous solution of graphene oxide, denoted as solution B, and continue to stir until uniformly mixed; 5)将搅拌均匀的溶液B加入到搅拌混合均匀的溶液A中,得到溶液C,并持续搅拌至混合均匀;5) Add the well-stirred solution B to the well-stirred solution A to obtain the solution C, and continue to stir until the well-mixed solution; 6)将十二烷基苯磺酸钠加入到上述搅拌混合均匀的溶液C中并加热进行反应,整个过程持续通入氮气并搅拌;6) Sodium dodecylbenzene sulfonate is added in the above-mentioned stirred and mixed solution C and heated to react, and the whole process continues to be fed with nitrogen and stirred; 7)待反应结束,将产物过滤、离心、洗涤并干燥,即得到氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料。7) After the reaction is completed, the product is filtered, centrifuged, washed and dried to obtain the graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material. 2.根据权利要求1所述的一种氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料的制备方法,其特征在于,步骤1)所述的葡萄糖溶液浓度为40mg/mL;步骤1)中水热反应的温度为180℃,时间为12h。2. the preparation method of a kind of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material according to claim 1, is characterized in that, step 1) described glucose solution concentration is 40mg/mL; Step 1) The temperature of the hydrothermal reaction is 180°C and the time is 12h. 3.根据权利要求1所述的一种氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料的制备方法,其特征在于,步骤2)中去离子水和无水乙醇的混合溶液中去离子水和无水乙醇的体积比为5:4,且每90mL去离子水和无水乙醇的混合溶液中加入0.2g碳微球。3. the preparation method of a kind of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material according to claim 1, is characterized in that, in step 2) in the mixed solution of deionized water and absolute ethanol The volume ratio of deionized water and absolute ethanol was 5:4, and 0.2 g of carbon microspheres was added to each 90 mL of the mixed solution of deionized water and absolute ethanol. 4.根据权利要求1所述的一种氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料的制备方法,其特征在于,步骤2)中硅烷偶联剂采用KH550,硅烷偶联剂和无水乙醇的混合溶液具体为:每20mL无水乙醇中加入5mL硅烷偶联剂。4. the preparation method of a kind of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material according to claim 1, is characterized in that, in step 2), silane coupling agent adopts KH550, silane coupling agent The specific mixing solution with absolute ethanol is as follows: 5 mL of silane coupling agent is added to every 20 mL of absolute ethanol. 5.根据权利要求1所述的一种氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料的制备方法,其特征在于,步骤2)中去离子水和无水乙醇的混合溶液与硅烷偶联剂和无水乙醇的混合溶液的体积比为18:5。5. the preparation method of a kind of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material according to claim 1, is characterized in that, the mixed solution of deionized water and absolute ethanol in step 2) and The volume ratio of the mixed solution of the silane coupling agent and absolute ethanol is 18:5. 6.根据权利要求1所述的一种氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料的制备方法,其特征在于,步骤2)中冷凝回流加热条件具体为:在60℃下冷凝回流12h。6. the preparation method of a kind of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material according to claim 1, is characterized in that, in step 2), condensation reflux heating condition is specially: at 60 ℃ Condensed and refluxed for 12h. 7.根据权利要求1所述的一种氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料的制备方法,其特征在于,步骤3)溶液A中改性碳微球的浓度为5mg/mL-8mg/mL,且甲基丙烯酸甲酯加入量为改性碳微球质量的0.2wt%。7. the preparation method of a kind of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material according to claim 1, is characterized in that, step 3) in solution A, the concentration of modified carbon microsphere is 5mg /mL-8mg/mL, and the amount of methyl methacrylate added was 0.2wt% of the mass of the modified carbon microspheres. 8.根据权利要求1所述的一种氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料的制备方法,其特征在于,步骤5)溶液C中氧化石墨烯与改性碳微球的质量比为1:5。8. the preparation method of a kind of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material according to claim 1, is characterized in that, step 5) in solution C, graphene oxide and modified carbon microsphere The mass ratio is 1:5. 9.根据权利要求1所述的一种氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料的制备方法,其特征在于,步骤5)中溶液A和溶液B之间的体积比为2:1。9. the preparation method of a kind of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material according to claim 1, is characterized in that, in step 5), the volume ratio between solution A and solution B is 2:1. 10.根据权利要求1所述的一种氧化石墨烯增强聚甲基丙烯酸甲酯/碳微球复合材料的制备方法,其特征在于,步骤6)中十二烷基苯磺酸钠加入质量与改性碳微球的质量比为1:40,步骤6)中反应温度为60℃,反应时间为12h。10. the preparation method of a kind of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material according to claim 1, is characterized in that, in step 6), sodium dodecyl benzene sulfonate adds mass and The mass ratio of the modified carbon microspheres was 1:40, the reaction temperature in step 6) was 60°C, and the reaction time was 12h.
CN202010663447.2A 2020-07-10 2020-07-10 A kind of preparation method of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material Active CN111777728B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010663447.2A CN111777728B (en) 2020-07-10 2020-07-10 A kind of preparation method of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010663447.2A CN111777728B (en) 2020-07-10 2020-07-10 A kind of preparation method of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material

Publications (2)

Publication Number Publication Date
CN111777728A CN111777728A (en) 2020-10-16
CN111777728B true CN111777728B (en) 2022-06-03

Family

ID=72768826

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010663447.2A Active CN111777728B (en) 2020-07-10 2020-07-10 A kind of preparation method of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material

Country Status (1)

Country Link
CN (1) CN111777728B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112724830A (en) * 2020-12-29 2021-04-30 广东绿色大地化工有限公司 Super-hydrophobic anti-fouling anti-icing water-based paint
CN113980718B (en) * 2021-11-19 2022-04-29 陕西科技大学 A kind of preparation method of carbon ball/two-dimensional covalent organic polymer nanoparticles

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105062621A (en) * 2015-08-17 2015-11-18 武汉理工大学 Graphene oxide-polymeric microsphere water-based lubricant additive and preparation method thereof
WO2017186127A1 (en) * 2016-04-26 2017-11-02 复旦大学 Method for preparing graphene-modified polymethyl methacrylate composite material having ultra-high conductivity
CN109913289A (en) * 2019-03-25 2019-06-21 陕西科技大学 A kind of preparation method of graphene oxide-coated carbon microsphere composite material
CN110628158A (en) * 2019-09-27 2019-12-31 陕西科技大学 A kind of preparation method of water-phase radical polymerization of polymethyl methacrylate/carbon microsphere nanocomposite with core-shell structure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105062621A (en) * 2015-08-17 2015-11-18 武汉理工大学 Graphene oxide-polymeric microsphere water-based lubricant additive and preparation method thereof
WO2017186127A1 (en) * 2016-04-26 2017-11-02 复旦大学 Method for preparing graphene-modified polymethyl methacrylate composite material having ultra-high conductivity
CN109913289A (en) * 2019-03-25 2019-06-21 陕西科技大学 A kind of preparation method of graphene oxide-coated carbon microsphere composite material
CN110628158A (en) * 2019-09-27 2019-12-31 陕西科技大学 A kind of preparation method of water-phase radical polymerization of polymethyl methacrylate/carbon microsphere nanocomposite with core-shell structure

Also Published As

Publication number Publication date
CN111777728A (en) 2020-10-16

Similar Documents

Publication Publication Date Title
CN105646944B (en) A kind of preparation method of organically modified molybdenum disulfide nanosheet
CN111777728B (en) A kind of preparation method of graphene oxide reinforced polymethyl methacrylate/carbon microsphere composite material
CN114163712B (en) A kind of graphene composite PE material and preparation method thereof
CN104559176A (en) Preparation method of three-dimensional reduced graphene oxide/polyaniline composite material
CN103627180B (en) Carbon nanotube grafting cage-type silsesquioxane modified silicon rubber and preparation method thereof
CN110628158A (en) A kind of preparation method of water-phase radical polymerization of polymethyl methacrylate/carbon microsphere nanocomposite with core-shell structure
CN110734642B (en) Insulating high-strength nano composite material and preparation method thereof
CN103627181B (en) Carbon nanotube grafted polydimethylsiloxane modified silicone rubber and preparation method thereof
CN113980359B (en) Modified MXene-loaded metal oxide composite and preparation method and application thereof
CN114437447B (en) A kind of degradable composite foam material with high mechanical properties and preparation method thereof
CN115418024A (en) Carbon nanotube/carbon black aggregate, preparation method thereof and high-performance tire tread rubber composition
CN107033266A (en) A kind of preparation method of high-dispersibility carbon nanotube/polystyrene nano composite material
CN105199104A (en) Polyetherimide in situ polymerization technology adopting p-phenylenediamine lossless modified carbon nano tube as heat conductive and antistatic medium
CN1919934A (en) Solvent-free inorganic nano particle fluid and preparation method thereof
CN104893246A (en) Preparation method of graphene-based hyperbranched perylene imide/epoxy composite
CN110511519A (en) Preparation method of carbon microsphere/polymethyl methacrylate/polyethyleneimine nanocomposite with double shell-core structure
CN109535581A (en) Carbon nano tube-doped polystyrene-based composite material and preparation method with core-shell structure
CN111662547A (en) Molybdenum disulfide quantum dot/graphene/polymer-based super-wear-resistant self-lubricating composite material and preparation method and application thereof
CN112852287A (en) Preparation method of nano silicon carbide loaded reduced graphene oxide compound modified thermosetting polyimide wear-resistant coating
CN115353922A (en) Carbon nitride quantum dot-based polyethylene glycol lubricating additive and preparation method thereof
CN101891936A (en) Preparation method of composite material based on epoxy resin and phosphazene nanotubes
CN103524791A (en) Method for preparing polyacrylic acid covalent functionalized carbon nano tube antistatic agent
CN114874406B (en) Multifunctional nano lubricating oil additive and preparation method and application thereof
CN110305448A (en) Preparation method of a six-membered heterocyclic covalently modified graphene oxide/epoxy resin composite
CN105669971B (en) Preparation method of in-situ polymerized carbon nanotube modified nylon composite material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant