WO2017186127A1 - Method for preparing graphene-modified polymethyl methacrylate composite material having ultra-high conductivity - Google Patents

Method for preparing graphene-modified polymethyl methacrylate composite material having ultra-high conductivity Download PDF

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WO2017186127A1
WO2017186127A1 PCT/CN2017/082040 CN2017082040W WO2017186127A1 WO 2017186127 A1 WO2017186127 A1 WO 2017186127A1 CN 2017082040 W CN2017082040 W CN 2017082040W WO 2017186127 A1 WO2017186127 A1 WO 2017186127A1
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expanded graphite
megic
egic
composite
graphene
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卢红斌
王鹏
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复旦大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives

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  • the mass to volume ratio of the oxidizing agent to the concentrated sulfuric acid is 1 g: (40-200) ml.
  • the EGIC modified without the silane coupling agent is not conducive to the entry of the MMA into the EGIC interlayer reaction, and thus the peeling of the graphene is not well achieved.
  • silane coupling agent MPS is not added, and the specific steps include:

Abstract

The present invention relates to a method for preparing a graphene-modified polymethyl methacrylate complex having ultra-high conductivity. The method comprises the following steps: (1) firstly, slightly oxidizing an expanded graphite to obtain an expanded graphite intercalation compound (EGIC); (2) modifying the EGIC with a silane coupling agent to obtain an mEGIC; (3) adding the mEGIC, methyl methacrylate and dibenzoyl peroxide to an 1-methyl-2-pyrrolidone solvent, stirring the mixture at room temperature for a period of time, and then warming to a reaction temperature for polymerization reaction; after the reaction, pouring the product into methanol for centrifugation, washing and vacuum drying, thus obtaining a graphene-modified polymethyl methacrylate complex. In the present invention, when the mEGIC content reaches 10wt%, the glass transition temperature of the complex can be increased to be 18°C higher than that of polymethyl methacrylate, the elastic storage modulus is increased by approximately 300%, and the electrical conductivity can reach 1700 S/m or more.

Description

一种超高电导率石墨烯改性聚甲基丙烯酸甲酯复合材料的制备方法Preparation method of ultra-high conductivity graphene modified polymethyl methacrylate composite material 技术领域Technical field
本发明涉及一种简单的石墨烯/聚合物复合物的制备方法，具体是一种硅烷化轻度氧化的石墨烯改性聚甲基丙烯酸甲酯复合物的制备方法，属于纳米复合材料领域。The invention relates to a simple preparation method of graphene/polymer composite, in particular to a preparation method of silanized lightly oxidized graphene modified polymethyl methacrylate composite, belonging to the field of nano composite materials.
背景技术Background technique
石墨烯是一种只有单原子厚度的二维碳纳米材料。因其具有的独特性质诸如很大的比表面积(2630m2g-1)，很高的杨氏模量(～1TPa)，超高的热传导率(5100Wm-1K-1)以及优良的电性能等受到许多研究者的青睐。石墨烯凭借其优良的综合性能使得其在电子器件、聚合物复合物等领域有着广泛的应用前景，尤其是在聚合物复合材料领域，石墨烯目前已成为最热门的高性能材料之一。Graphene is a two-dimensional carbon nanomaterial with a single atomic thickness. Due to its unique properties such as large specific surface area (2630m 2 g -1 ), high Young's modulus (~1TPa), high thermal conductivity (5100Wm -1 K -1 ) and excellent electrical properties Etc. is favored by many researchers. Graphene has broad application prospects in the fields of electronic devices and polymer composites due to its excellent comprehensive properties. Especially in the field of polymer composites, graphene has become one of the most popular high-performance materials.
然而，若要实现石墨烯对聚合物综合性能的改善、制得性能优异的石墨烯-聚合物复合材料，核心的关键问题在于解决石墨烯在聚合物基体中的分散以及石墨烯与聚合物之间的界面相互作用。在过去许多研究中，人们通常需要首先制备石墨烯，然后再对石墨烯进行各种改性，最后再与聚合物进行复合。这种制备方法流程长，操作复杂，并且随着石墨烯含量的增加，复合材料材料中的分散效果显著恶化，这为其实际的规模化应用提出了挑战。However, in order to achieve the improvement of the comprehensive properties of the graphene and the graphene-polymer composite with excellent performance, the key issue of the core is to solve the dispersion of graphene in the polymer matrix and the graphene and polymer. Interfacial interactions. In many studies in the past, it was common to first prepare graphene, then various modifications to graphene, and finally to polymerize with the polymer. The preparation method has a long process and complicated operation, and as the graphene content increases, the dispersion effect in the composite material is significantly deteriorated, which poses a challenge for its practical scale application.
聚甲基丙烯酸甲酯(PMMA)是广泛应用的一类高分子材料，具有极好的透明性、突出的耐老化性以及期望的机械强度，并且价格相对低廉。在已有的一些工作中，人们用已经尝试用石墨烯来改进聚甲基丙烯酸甲酯的力学和电学性能。然而，虽然改性后的PMMA复合材料的许多性能显示出改进趋势，但大多方法工艺流程长、操作复杂，无法满足工业应用的实际需要。本发明提出一种简单、有效的制备石墨烯/聚甲基丙烯酸甲酯复合物的新方法，该方法无须事先制备石墨烯，而是直接采用硅烷偶链剂修饰的、轻度氧化的膨胀石墨(mEGIC)，并将之与MMA单体直接混合后进行原位聚合，复合材料中的膨胀石墨可以在随后的挤出或混合过程中得到剥离、并实现均匀分散，极大地简化了复合材料的制备工艺流程，也使其得以真正实现规模化应用。在聚合过程中，由于膨胀石墨表面存在硅烷偶联剂分子，因而MMA可以渗透进入mEGIC层间发生层间聚合反应，并通过MMA在mEGIC层间的聚合反应自发将mEGIC剥离成石墨烯，而且，石墨烯的剥离还会在后续挤出和混合过程中进一步得到强化和均匀化，因而从根本上解决了石墨烯在PMMA中的分散和加工等问题。此外，由于部分PMMA分子链会在聚合过程中接枝到mEGIC上，强化了石墨烯与PMMA的界面相互作用，也使得制备的PMMA复合材料表现出优异的力学和电学性质。该方法制备PMMA-石墨 烯复合材料的工艺流程短、操作简便，具有良好的实际应用价值。Polymethyl methacrylate (PMMA) is a widely used polymer material with excellent transparency, outstanding aging resistance, and desired mechanical strength, and is relatively inexpensive. In some of the work already done, graphene has been tried to improve the mechanical and electrical properties of polymethyl methacrylate. However, although many properties of the modified PMMA composite show an improvement trend, most of the methods have long process flow and complicated operation, and cannot meet the actual needs of industrial applications. The invention provides a simple and effective new method for preparing graphene/polymethyl methacrylate composite, which does not need to prepare graphene in advance, but directly uses silane coupling agent modified, lightly oxidized expanded graphite. (mEGIC), and directly mixed with MMA monomer for in-situ polymerization, the expanded graphite in the composite can be peeled off during the subsequent extrusion or mixing process, and achieve uniform dispersion, greatly simplifying the composite The preparation process also enables it to truly achieve scale application. During the polymerization process, due to the presence of silane coupling agent molecules on the surface of the expanded graphite, MMA can penetrate into the mEGIC layer to form interlayer polymerization, and spontaneously remove mEGIC into graphene by MMA polymerization between mEGIC layers, and The stripping of graphene is further strengthened and homogenized in the subsequent extrusion and mixing processes, thus fundamentally solving the problems of dispersion and processing of graphene in PMMA. In addition, since some of the PMMA molecular chains are grafted onto mEGIC during polymerization, the interfacial interaction between graphene and PMMA is enhanced, and the prepared PMMA composites exhibit excellent mechanical and electrical properties. This method prepares PMMA-graphite The olefin composite material has short process flow, simple operation and good practical application value.
发明内容Summary of the invention
本发明的目的在于提供一种能够显著改善PMMA综合性能的一种硅烷化低氧化程度石墨改性聚甲基丙烯酸甲酯复合物的制备方法。It is an object of the present invention to provide a method for preparing a silanized low oxidation degree graphite modified polymethyl methacrylate composite which can significantly improve the overall performance of PMMA.
本发明是采用硅烷化的低氧化程度膨胀石墨(mEGIC)通过原位聚合方法改善PMMA的性能。当mEGIC含量达到10wt％，复合材料的玻璃化温度相比纯PMMA提高了18℃，弹性储能模量提高约300％，电导率达到惊人的1719S/m，是目前电导率最高的聚合物复合物之一。The present invention improves the performance of PMMA by in-situ polymerization using silanized low oxidation grade expanded graphite (mEGIC). When the mEGIC content reaches 10wt%, the glass transition temperature of the composite is 18°C higher than that of pure PMMA, the elastic storage modulus is increased by about 300%, and the electrical conductivity reaches a staggering 1719S/m. It is the polymer composite with the highest conductivity. One of the things.
本发明是采用如下技术方案实现的：The invention is implemented by the following technical solutions:
本发明第一方面提供了一种硅烷化低氧化程度石墨改性聚甲基丙烯酸甲酯复合物的制备方法，具体步骤如下：The first aspect of the invention provides a method for preparing a silicided low oxidation degree graphite modified polymethyl methacrylate composite, the specific steps are as follows:
(1)将1～3g膨胀石墨用200～600mL浓硫酸和1～3g强氧化剂进行轻微氧化；(1) 1 to 3 g of expanded graphite is slightly oxidized with 200 to 600 mL of concentrated sulfuric acid and 1 to 3 g of strong oxidizing agent;
(2)将轻微氧化的膨胀石墨(EGIC)加入到50～150mL去离子水和100～300mL乙醇的混合溶液中在60～70℃下搅拌均匀，得到EGIC的混合溶液；将2.5～7.5mL硅烷偶联剂在pH＝4～5的40～120mL的水溶液中搅拌水解；将彻底水解后的硅烷偶联剂溶液倒入上述EGIC的混合溶液中，在60～70℃反应2小时，最后将产物用甲醇和水洗涤抽滤得到mEGIC；(2) Add slightly oxidized expanded graphite (EGIC) to a mixed solution of 50-150 mL of deionized water and 100-300 mL of ethanol, and mix well at 60-70 ° C to obtain a mixed solution of EGIC; 2.5 to 7.5 mL of silane The coupling agent is stirred and hydrolyzed in an aqueous solution of 40 to 120 mL of pH=4 to 5; the completely hydrolyzed silane coupling agent solution is poured into the mixed solution of the above EGIC, and reacted at 60 to 70 ° C for 2 hours, and finally the product is obtained. Washing with methanol and water to obtain mEGIC;
(3)将mEGIC、甲基丙烯酸甲酯(MMA)和过氧化二苯甲酰(BPO)加入到NMP溶剂中，于常温下搅拌一段时间后，升温到70～90℃反应7～12小时，将产物倒入甲醇中经过离心、洗涤和真空干燥，得到改性的PMMA复合材料。其中：甲基丙烯酸甲酯(MMA)和过氧化二苯甲酰(BPO)的质量比为100～300：1。(3) adding mEGIC, methyl methacrylate (MMA) and dibenzoyl peroxide (BPO) to the NMP solvent, stirring at room temperature for a period of time, and then raising the temperature to 70 to 90 ° C for 7 to 12 hours. The product was poured into methanol, centrifuged, washed and vacuum dried to obtain a modified PMMA composite. Among them: the mass ratio of methyl methacrylate (MMA) and dibenzoyl peroxide (BPO) is 100 to 300:1.
在另一优选例中，所述硅烷化低氧化程度石墨改性聚甲基丙烯酸甲酯复合物的制备方法包括步骤：In another preferred embodiment, the method for preparing the silanized low oxidation degree graphite modified polymethyl methacrylate composite comprises the steps of:
(a)将膨胀石墨、浓硫酸与氧化剂混合，制得低氧化程度的膨胀石墨；(a) mixing expanded graphite, concentrated sulfuric acid and an oxidizing agent to obtain expanded graphite having a low degree of oxidation;
(b)有机溶剂中，将步骤(a)得到的低氧化程度的膨胀石墨与硅烷偶联剂混合，制得mEGIC；和(b) in an organic solvent, mixing the low-oxidation expanded graphite obtained in the step (a) with a silane coupling agent to obtain mEGIC;
(c)有机溶剂中，将mEGIC、甲基丙烯酸甲酯(MMA)和过氧化二苯甲酰(BPO)混合，制得改性的聚甲基丙烯酸甲酯复合材料。(c) In an organic solvent, mEGIC, methyl methacrylate (MMA) and dibenzoyl peroxide (BPO) are mixed to prepare a modified polymethyl methacrylate composite.
在另一优选例中，步骤(1)中所述膨胀石墨为热膨胀石墨或化学膨胀石墨。In another preferred embodiment, the expanded graphite in the step (1) is thermally expanded graphite or chemically expanded graphite.
在另一优选例中，，步骤(1)中所用氧化剂为高锰酸钾、重铬酸钾、浓硫酸/浓硝酸混合物 (体积比1-5:1)、高铁酸钾，氧化剂与原料膨胀石墨质量比为1-5：1。In another preferred embodiment, the oxidizing agent used in the step (1) is potassium permanganate, potassium dichromate, concentrated sulfuric acid/concentrated nitric acid mixture (Volume ratio 1-5:1), potassium ferrate, the mass ratio of oxidant to raw material expanded graphite is 1-5:1.
在另一优选例中，所述步骤(1)或步骤(a)中，所述氧化剂选自下组：高锰酸钾、重铬酸钾、浓硫酸/浓硝酸混合物(体积比1-5:1)、高铁酸钾、或其组合。In another preferred embodiment, in the step (1) or the step (a), the oxidizing agent is selected from the group consisting of potassium permanganate, potassium dichromate, and concentrated sulfuric acid/concentrated nitric acid (volume ratio 1-5). : 1), potassium ferrate, or a combination thereof.
在另一优选例中，所述步骤(1)或步骤(a)中，所述氧化剂与浓硫酸的质量体积比为1g：(40-200)ml。In another preferred embodiment, in the step (1) or the step (a), the mass to volume ratio of the oxidizing agent to the concentrated sulfuric acid is 1 g: (40-200) ml.
在另一优选例中，所述步骤(3)或步骤(c)中，所述mEGIC与甲基丙烯酸甲酯的质量比为1：(10-100)。In another preferred embodiment, in the step (3) or the step (c), the mass ratio of the mEGIC to methyl methacrylate is 1: (10-100).
在另一优选例中，步骤(2)中所用硅烷偶联剂为3-(甲基丙烯酰氧)丙基三甲氧基硅烷(MPS)、乙烯基三甲氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷或乙烯基三乙氧基硅烷等含有双键的硅烷偶联剂中任一种。In another preferred embodiment, the silane coupling agent used in the step (2) is 3-(methacryloyloxy)propyltrimethoxysilane (MPS), vinyltrimethoxysilane, vinyltris(2-) Any of silane coupling agents containing a double bond such as methoxyethoxysilane or vinyltriethoxysilane.
在另一优选例中，步骤(2)中所用硅烷偶联剂溶液的浓度为0.02～0.2g/mL。In another preferred embodiment, the concentration of the silane coupling agent solution used in the step (2) is 0.02 to 0.2 g/mL.
在另一优选例中，步骤(3)中常温下搅拌一段时间是指在常温下搅拌0.1～10小时。In another preferred embodiment, stirring in the step (3) at a normal temperature for a period of time means stirring at normal temperature for 0.1 to 10 hours.
在另一优选例中，所述步骤(c)中，所述有机溶剂选自下组：N-甲基吡咯烷酮(NMP)、N、N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、或其组合。In another preferred embodiment, in the step (c), the organic solvent is selected from the group consisting of N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), and dimethylene. Sulfone (DMSO), or a combination thereof.
在另一优选例中，石墨烯在复合材料中的含量为0.1-15wt％，较佳地为1-10wt％。In another preferred embodiment, the graphene is contained in the composite in an amount of from 0.1 to 15% by weight, preferably from 1 to 10% by weight.
需注意的是，上述机理性的描述不作为对本发明保护范围的限制，本发明中的制备方法主要由所述步骤进行限定。It should be noted that the above-described mechanistic description is not intended to limit the scope of the present invention, and the preparation method in the present invention is mainly defined by the steps.
本发明的有益效果在于：The beneficial effects of the invention are:
本发明直接将硅烷偶联剂修饰后的轻微氧化的膨胀石墨(mEGIC)与MMA进行原位聚合就能得到性能优异的聚合物复合材料。当mEGIC含量达到10wt％时，复合材料的玻璃化温度比纯PMMA提高18℃，弹性储能模量提高约300％，电导率可达1700S/m以上，是目前电导率最高的聚合物复合材料之一。此方法无须首先制备石墨烯，制备流程短、操作简单，具有良好的工业应用价值。In the present invention, the slightly oxidized expanded graphite (mEGIC) modified by the silane coupling agent is directly polymerized with MMA to obtain a polymer composite having excellent properties. When the content of mEGIC reaches 10wt%, the glass transition temperature of the composite is 18°C higher than that of pure PMMA, the elastic storage modulus is increased by about 300%, and the electrical conductivity is up to 1700S/m. It is the polymer composite with the highest conductivity. one. The method does not need to prepare graphene first, has short preparation process, simple operation and good industrial application value.
附图说明DRAWINGS
图1为轻微氧化的膨胀石墨(EGIC)和经硅烷偶联剂修饰后的膨胀石墨mEGIC的热失重(TGA)曲线。Figure 1 is a graph showing the thermogravimetric (TGA) curves of slightly oxidized expanded graphite (EGIC) and expanded graphite mEGIC modified with a silane coupling agent.
图2为含有1wt％mEGIC的PMMA复合材料的超薄切片透射电镜图。Figure 2 is a transmission electron micrograph of an ultra-thin section of a PMMA composite containing 1 wt% mEGIC.
图3为含有4wt％mEGIC的PMMA复合材料的超薄切片透射电镜图。 Figure 3 is a transmission electron micrograph of an ultra-thin section of a PMMA composite containing 4 wt% mEGIC.
图4为含有10wt％mEGIC的PMMA复合材料的超薄切片透射电镜图。Figure 4 is a transmission electron micrograph of an ultra-thin section of a PMMA composite containing 10 wt% mEGIC.
图5为含有1wt％EGIC的PMMA复合材料的超薄切片透射电镜图。Figure 5 is a transmission electron micrograph of an ultra-thin section of a PMMA composite containing 1 wt% EGIC.
图6为含有4wt％EGIC的PMMA复合材料的超薄切片透射电镜图。Figure 6 is a transmission electron micrograph of an ultra-thin section of a PMMA composite containing 4 wt% EGIC.
图7为含有10wt％EGIC的PMMA复合材料的超薄切片透射电镜图。Figure 7 is a transmission electron micrograph of an ultra-thin section of a PMMA composite containing 10 wt% EGIC.
图8为含有1、4、10wt％mEGIC的PMMA复合材料的动态热机械分析(DMA)曲线。Figure 8 is a dynamic thermomechanical analysis (DMA) curve of a PMMA composite containing 1, 4, 10 wt% mEGIC.
图9为含有1、4、10wt％EGIC的PMMA复合材料的动态热机械分析(DMA)曲线。Figure 9 is a dynamic thermomechanical analysis (DMA) curve of a PMMA composite containing 1, 4, 10 wt% EGIC.
具体实施方式detailed description
以下实施例将结合附图对本发明作进一步的说明。应当理解，这些实例仅用于说明本发明而不用于限制本发明的范围。对于本领域的技术人员在不违背本发明精神和保护范围的情况下做出的其它的变化和修改，仍包括在本发明保护范围之内。The invention will be further illustrated by the following examples in conjunction with the accompanying drawings. It is to be understood that the examples are only illustrative of the invention and are not intended to limit the scope of the invention. Other changes and modifications made by those skilled in the art without departing from the spirit and scope of the invention are still included in the scope of the invention.
下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。除非另外说明，否则百分比和份数是重量百分比和重量份数。The experimental methods in the following examples which do not specify the specific conditions are usually in accordance with conventional conditions or according to the conditions recommended by the manufacturer. Unless otherwise stated, percentages and parts are by weight and parts by weight.
以下实施例中所用的实验材料和试剂如无特别说明均可从市售渠道获得。The experimental materials and reagents used in the following examples are available from commercially available sources unless otherwise specified.
术语说明Terminology
除非另外定义，否则本文中所用的全部技术与科学术语均具有如本发明所属领域的普通技术人员通常理解的相同含义。All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise defined.
如本文所用，在提到具体列举的数值中使用时，术语“约”意指该值可以从列举的值变动不多于1％。例如，如本文所用，表述“约100”包括99和101和之间的全部值(例如，99.1、99.2、99.3、99.4等)。As used herein, when used in reference to a particular recited value, the term "about" means that the value can vary by no more than 1% from the recited value. For example, as used herein, the expression "about 100" includes all values between 99 and 101 and (eg, 99.1, 99.2, 99.3, 99.4, etc.).
如本文所用，术语“含有”或“包括(包含)”可以是开放式、半封闭式和封闭式的。换言之，所述术语也包括“基本上由…构成”、或“由…构成”。As used herein, the terms "containing" or "including" may be open, semi-closed, and closed. In other words, the terms also include "consisting essentially of," or "consisting of."
如本文所用，所述“低氧化程度的膨胀石墨”、“轻微氧化的膨胀石墨”、“EGIC”可互换使用，具有相同含义。As used herein, the "low oxidized expanded graphite", "slightly oxidized expanded graphite", "EGIC" are used interchangeably and have the same meaning.
如本文所用，所述“mEGIC”、“硅烷偶链剂修饰的轻度氧化的膨胀石墨”、“经修饰的膨胀石墨”可互换使用，具有相同含义。As used herein, the "mEGIC", "silane-coupled agent modified lightly oxidized expanded graphite", "modified expanded graphite" are used interchangeably and have the same meaning.
原料与通用方法Raw materials and general methods
膨胀石墨：本发明实施例中，所述原料膨胀石墨是按照传统热膨胀石墨制备方法或发明 人之前专利技术(卢红斌、张佳佳、陈宇菲，一种常温常压下直接制备膨胀石墨或石墨烯的方法，CN201510792745.0)和论文公开的膨胀石墨室温制备技术(林珊、董雷、张佳佳、卢红斌*,Room-Temperature Intercalation and～1000-Fold Chemical Expansion for Scalable Preparation of High-Quality Graphene,Chemistry of Materials 2016,28,2138-2146)所述制备。Expanded graphite: In the embodiment of the invention, the raw material expanded graphite is a conventional heat expansion graphite preparation method or invention Previous patented technology (Lu Hongbin, Zhang Jiajia, Chen Yufei, a method for directly preparing expanded graphite or graphene under normal temperature and pressure, CN201510792745.0) and expanded graphite room temperature preparation technology (Lin Shan, Dong Lei, Zhang Jiajia, Lu Hongbin *, Room-Temperature Intercalation and ~1000-Fold Chemical Expansion for Scalable Preparation of High-Quality Graphene, Chemistry of Materials 2016, 28, 2138-2146).
储能模量：Storage modulus:
DMA分析曲线测试方法：我们用动态力学分析仪(DMA，厂家：Mettler Toledo，型号：SDTA861e)测试复合物的弹性储能模量，我们选取拉伸模式，样品尺寸为长：10.5mm，宽：6mm，高：0.5mm。测试频率为1Hz，测试温度为40到140℃。DMA analysis curve test method: We use the dynamic mechanical analyzer (DMA, manufacturer: Mettler Toledo, model: SDTA861e) to test the elastic storage modulus of the composite, we choose the tensile mode, the sample size is long: 10.5mm, width: 6mm, height: 0.5mm. The test frequency is 1 Hz and the test temperature is 40 to 140 °C.
实施例1：复合材料1Example 1: Composite 1
将2g膨胀石墨、350mL浓硫酸、2g高锰酸钾混合后加入到500mL三口烧瓶中，在35℃下反应1小时，得到低氧化程度的膨胀石墨(EGIC)。2 g of expanded graphite, 350 mL of concentrated sulfuric acid, and 2 g of potassium permanganate were mixed, and the mixture was placed in a 500 mL three-necked flask, and reacted at 35 ° C for 1 hour to obtain expanded graphite (EGIC) having a low degree of oxidation.
取上述EGIC的一半加入到含有50mL去离子水和100mL乙醇的混合溶剂的三口烧瓶中，在62℃下搅拌。然后将2.5mL硅烷偶联剂MPS加入到pH＝4的40mL去离子水中搅拌水解，待MPS水解完后，加入到上述EGIC的混合溶液中在62℃下继续反应2h。产物用100mL和200mL去离子水洗涤后抽滤，得到改性后的mEGIC。Half of the above EGIC was added to a three-necked flask containing a mixed solvent of 50 mL of deionized water and 100 mL of ethanol, and stirred at 62 °C. Then, 2.5 mL of the silane coupling agent MPS was added to 40 mL of deionized water of pH=4 to stir and hydrolyze. After the hydrolysis of the MPS was completed, the mixture was added to the above mixed solution of EGIC and the reaction was continued at 62 ° C for 2 hours. The product was washed with 100 mL and 200 mL of deionized water and suction filtered to give the modified mEGIC.
将0.5g上述mEGIC、30g MMA、0.15g BPO加入到含有100mL NMP溶剂的500mL三口烧瓶中，在常温和氮气保护下搅拌1h。然后，升温至80℃反应7h后结束。将反应后产物倒入500mL甲醇中，有黑色固体颗粒产生。离心分离，留取下层沉淀，用乙醇和水洗涤多次后将产物于80℃鼓风烘箱中干燥24小时，得到黑色粉末状固体，即为目标产物硅烷化石墨烯改性的PMMA复合材料，其中，石墨烯在复合材料中的含量为1wt％。0.5 g of the above mEGIC, 30 g of MMA, and 0.15 g of BPO were placed in a 500 mL three-necked flask containing 100 mL of NMP solvent, and stirred at room temperature under a nitrogen atmosphere for 1 hour. Then, the temperature was raised to 80 ° C and the reaction was completed for 7 hours. The product after the reaction was poured into 500 mL of methanol, and black solid particles were produced. The mixture was centrifuged, and the lower layer was precipitated. After washing with ethanol and water for several times, the product was dried in a blast oven at 80 ° C for 24 hours to obtain a black powdery solid, which was a target product silanized graphene-modified PMMA composite material. Among them, the content of graphene in the composite material is 1% by weight.
图1是EGIC和mEGIC的热失重曲线，可以看到由于MPS接枝到EGIC的含氧官能团中使得mEGIC起始分解温度提高30℃左右。Figure 1 is a graph showing the thermogravimetric curves of EGIC and mEGIC. It can be seen that the initial decomposition temperature of mEGIC is increased by about 30 °C due to the grafting of MPS into the oxygen-containing functional group of EGIC.
图2经过mEGIC改性后复合材料的超薄切边透射电镜图，可以看出石墨烯在复合物中分散良好。Figure 2 shows the ultra-thin trimming transmission electron micrograph of the composite after modification by mEGIC. It can be seen that graphene is well dispersed in the composite.
图8为各组mEGIC改性复合材料的DMA图，可以看到当mEGIC含量为1wt％时，复合材料的储能模量增大26％。 Figure 8 is a DMA diagram of each group of mEGIC modified composites. It can be seen that when the mEGIC content is 1 wt%, the storage modulus of the composite increases by 26%.
实施例2：复合材料2Example 2: Composite 2
同实施例1，不同之处在于，用重铬酸钾替换高锰酸钾，制得轻度氧化的膨胀石墨。包括步骤：The same as in Example 1, except that potassium permanganate was replaced with potassium dichromate to obtain slightly oxidized expanded graphite. Including steps:
将2g膨胀石墨、350mL浓硫酸、2g重铬酸钾混合后加入到500mL三口烧瓶中，在35℃下反应1小时，得到轻度氧化的膨胀石墨(EGIC)。2 g of expanded graphite, 350 mL of concentrated sulfuric acid, and 2 g of potassium dichromate were mixed, and the mixture was placed in a 500 mL three-necked flask, and reacted at 35 ° C for 1 hour to obtain slightly oxidized expanded graphite (EGIC).
取上述EGIC的一半加入到含有50mL去离子水和100mL乙醇的混合溶剂的三口烧瓶中，在62℃下搅拌。然后将2.5mL硅烷偶联剂(乙烯基三甲氧基硅烷)加入到pH＝4的40mL去离子水中搅拌水解，待硅烷偶联剂水解完后，加入到上述EGIC的混合溶液中在62℃下继续反应2h。产物用100mL和200mL去离子水洗涤后抽滤，得到改性后的mEGIC。Half of the above EGIC was added to a three-necked flask containing a mixed solvent of 50 mL of deionized water and 100 mL of ethanol, and stirred at 62 °C. Then, 2.5 mL of a silane coupling agent (vinyltrimethoxysilane) was added to 40 mL of deionized water of pH=4 to stir and hydrolyze. After the silane coupling agent was hydrolyzed, it was added to the above mixed solution of EGIC at 62 ° C. Continue to react for 2 h. The product was washed with 100 mL and 200 mL of deionized water and suction filtered to give the modified mEGIC.
将0.5g上述mEGIC、30g MMA、0.15g BPO加入到含有100mL NMP溶剂的500mL三口烧瓶中，先在常温下，氮气保护中搅拌4h。然后，升温至80℃反应12h后结束。将反应后产物倒入500mL甲醇中，有黑色固体颗粒产生。离心分离，留取下层沉淀，用乙醇和水洗涤多次后将产物于80℃鼓风烘箱中干燥24小时，得到黑色粉末状固体，即为目标产物硅烷化石墨烯改性的PMMA复合材料，其中，石墨烯在复合材料中的含量为1wt％。0.5 g of the above mEGIC, 30 g of MMA, and 0.15 g of BPO were placed in a 500 mL three-necked flask containing 100 mL of NMP solvent, and stirred at room temperature for 4 hours under nitrogen atmosphere. Then, the temperature was raised to 80 ° C and the reaction was completed for 12 hours. The product after the reaction was poured into 500 mL of methanol, and black solid particles were produced. The mixture was centrifuged, and the lower layer was precipitated. After washing with ethanol and water for several times, the product was dried in a blast oven at 80 ° C for 24 hours to obtain a black powdery solid, which was a target product silanized graphene-modified PMMA composite material. Among them, the content of graphene in the composite material is 1% by weight.
本实施例所制得复合材料结构性能与实施例1相当。The structural properties of the composite material produced in this example were comparable to those of Example 1.
实施例3:复合材料3Example 3: Composite 3
1)将1g膨胀石墨、200mL浓硫酸、1g高锰酸钾混合后加入到500mL三口烧瓶中，在35℃下反应1小时，得到轻微氧化的膨胀石墨(EGIC)。1) 1 g of expanded graphite, 200 mL of concentrated sulfuric acid, and 1 g of potassium permanganate were mixed, and then added to a 500 mL three-necked flask, and reacted at 35 ° C for 1 hour to obtain slightly oxidized expanded graphite (EGIC).
2)将上述EGIC加入含有50mL去离子水和100mL乙醇的混合溶剂的三口烧瓶中，在62℃下搅拌。然后将3mL硅烷偶联剂(乙烯基三(2-甲氧基乙氧基)硅烷)加入到pH＝5的50mL去离子水中搅拌水解，待硅烷偶联剂水解完后加入到上述EGIC的混合溶液中在62℃下继续反应2h。产物用100mL和200mL去离子水洗涤后，抽滤得到改性后的mEGIC。2) The above EGIC was placed in a three-necked flask containing a mixed solvent of 50 mL of deionized water and 100 mL of ethanol, and stirred at 62 °C. Then, 3 mL of a silane coupling agent (vinyltris(2-methoxyethoxy)silane) was added to 50 mL of deionized water at pH=5 to stir and hydrolyze, and after the hydrolysis of the silane coupling agent was completed, the mixture was added to the above EGIC. The reaction was continued at 62 ° C for 2 h in the solution. The product was washed with 100 mL and 200 mL of deionized water, and filtered to give a modified mEGIC.
3)将1g上述mEGIC、30g MMA、0.15g BPO加入含有100mL NMP溶剂的500mL三口烧瓶中，在常温和氮气保护中搅拌5h。然后，升温至80℃反应7h后结束反应。接着，将产物倒入500mL甲醇中，有黑色固体颗粒产生。离心分离，留取下层沉淀，用乙醇和水洗涤多次后将产物于80℃鼓风烘箱中干燥24小时，得到黑色粉末状固体，即为目标产物硅烷化石墨烯改性PMMA复合材料。石墨烯在复合材料中的含量为4wt％。3) 1 g of the above mEGIC, 30 g of MMA, and 0.15 g of BPO were placed in a 500 mL three-necked flask containing 100 mL of NMP solvent, and stirred for 5 hours under normal temperature and nitrogen gas protection. Then, the reaction was heated to 80 ° C for 7 hours, and the reaction was terminated. Next, the product was poured into 500 mL of methanol, and black solid particles were produced. The mixture was centrifuged, and the lower layer precipitate was taken. After washing with ethanol and water for several times, the product was dried in a blast oven at 80 ° C for 24 hours to obtain a black powdery solid, which was the target product silylated graphene-modified PMMA composite. The content of graphene in the composite was 4% by weight.
本实施例mEGIC与EGIC的热失重曲线也为图1所示。复合材料的透射电镜结果如图3所示，可以看出石墨烯在复合物中具有良好的分散性。复合材料的DMA结果如图8所示，可以看到复合材料储能模量增加约100％。 The thermogravimetric curves of mEGIC and EGIC in this embodiment are also shown in Fig. 1. The results of TEM of the composite material are shown in Fig. 3. It can be seen that graphene has good dispersibility in the composite. The DMA results for the composites are shown in Figure 8. It can be seen that the composite storage modulus increases by about 100%.
实施例4：复合材料4Example 4: Composite 4
1)将1g膨胀石墨、200mL浓硫酸、1g高铁酸钾混合后加入到500mL三口烧瓶中，在35℃下反应1小时，得到轻微氧化的膨胀石墨(EGIC)。1) 1 g of expanded graphite, 200 mL of concentrated sulfuric acid, and 1 g of potassium ferrate were mixed, and then added to a 500 mL three-necked flask, and reacted at 35 ° C for 1 hour to obtain slightly oxidized expanded graphite (EGIC).
2)将上述EGIC加入含有50mL去离子水和100mL乙醇的混合溶剂的三口烧瓶中，在62℃下搅拌。然后将3mL硅烷偶联剂(乙烯基三(2-甲氧基乙氧基)硅烷)加入到pH＝5的50mL去离子水中搅拌水解，待硅烷偶联剂水解完后加入到上述EGIC的混合溶液中在62℃下继续反应2h。产物用100mL和200mL去离子水洗涤后，抽滤得到改性后的mEGIC2) The above EGIC was placed in a three-necked flask containing a mixed solvent of 50 mL of deionized water and 100 mL of ethanol, and stirred at 62 °C. Then, 3 mL of a silane coupling agent (vinyltris(2-methoxyethoxy)silane) was added to 50 mL of deionized water at pH=5 to stir and hydrolyze, and after the hydrolysis of the silane coupling agent was completed, the mixture was added to the above EGIC. The reaction was continued at 62 ° C for 2 h in the solution. The product was washed with 100 mL and 200 mL of deionized water, and filtered to obtain a modified mEGIC.
3)将1g上述mEGIC、30g MMA、0.15g BPO加入含有100mL NMP溶剂的500mL三口烧瓶中，在常温和氮气保护中搅拌0.1h。然后，升温至80℃反应7h后结束反应。接着，将产物倒入500mL甲醇中，有黑色固体颗粒产生。离心分离，留取下层沉淀，用乙醇和水洗涤多次后将产物于80℃鼓风烘箱中干燥24小时，得到黑色粉末状固体，即为目标产物硅烷化石墨烯改性PMMA复合材料。石墨烯在复合材料中的含量为4wt％。3) 1 g of the above mEGIC, 30 g of MMA, and 0.15 g of BPO were placed in a 500 mL three-necked flask containing 100 mL of NMP solvent, and stirred for 0.1 h at room temperature under nitrogen atmosphere. Then, the reaction was heated to 80 ° C for 7 hours, and the reaction was terminated. Next, the product was poured into 500 mL of methanol, and black solid particles were produced. The mixture was centrifuged, and the lower layer precipitate was taken. After washing with ethanol and water for several times, the product was dried in a blast oven at 80 ° C for 24 hours to obtain a black powdery solid, which was the target product silylated graphene-modified PMMA composite. The content of graphene in the composite was 4% by weight.
本实施例所制得复合材料的结构性能与实施例3相当。The structural properties of the composite material produced in this example were comparable to those of Example 3.
实施例5：复合材料5Example 5: Composite 5
1)将2g膨胀石墨、350mL浓硫酸、2g高锰酸钾混合后加入到500mL三口烧瓶中，在35℃下反应1小时，得到低氧化程度的膨胀石墨(EGIC)。1) 2 g of expanded graphite, 350 mL of concentrated sulfuric acid, and 2 g of potassium permanganate were mixed, and then added to a 500 mL three-necked flask, and reacted at 35 ° C for 1 hour to obtain expanded graphite (EGIC) having a low degree of oxidation.
2)将上述EGIC加入到含有50mL去离子水和100mL乙醇的混合溶剂的三口烧瓶中，在62℃下搅拌。然后将16mL硅烷偶联剂(乙烯基三甲氧基硅烷)加入到pH＝5的80mL去离子水中搅拌水解，待硅烷偶联剂水解完后加入到上述EGIC的混合溶液中在62℃下继续反应2h。产物用100mL和200mL去离子水洗涤后，抽滤得到改性后的mEGIC。2) The above EGIC was placed in a three-necked flask containing a mixed solvent of 50 mL of deionized water and 100 mL of ethanol, and stirred at 62 °C. Then, 16 mL of a silane coupling agent (vinyltrimethoxysilane) was added to 80 mL of deionized water at pH=5 to stir and hydrolyze. After the hydrolysis of the silane coupling agent, the reaction solution was added to the above EGIC mixed solution to continue the reaction at 62 ° C. 2h. The product was washed with 100 mL and 200 mL of deionized water, and filtered to give a modified mEGIC.
3)将1.5g上述mEGIC、30g MMA、0.15g BPO加入含有100mL NMP溶剂的500mL三口烧瓶中，在常温和氮气保护下搅拌10h，然后升温至80℃反应7h后结束反应。接着，将产物倒入500mL甲醇中，有黑色固体颗粒产生。离心分离，留取下层沉淀，用乙醇和水洗涤多次后将产物于80℃鼓风烘箱中干燥24小时，得到黑色粉末状固体，即为目标产物硅烷化石墨烯改性的PMMA复合材料。石墨烯在复合材料中的含量为10wt％。3) 1.5 g of the above mEGIC, 30 g of MMA, and 0.15 g of BPO were placed in a 500 mL three-necked flask containing 100 mL of NMP solvent, stirred at room temperature under nitrogen for 10 h, and then heated to 80 ° C for 7 h to terminate the reaction. Next, the product was poured into 500 mL of methanol, and black solid particles were produced. The mixture was centrifuged, and the lower layer precipitate was taken. After washing a plurality of times with ethanol and water, the product was dried in a blast oven at 80 ° C for 24 hours to obtain a black powdery solid, which was a target product silylated graphene-modified PMMA composite. The content of graphene in the composite was 10% by weight.
本实施例mEGIC与EGIC的热失重曲线如图1所示。复合材料的透射电镜结果如图4所示，可以看出石墨烯在复合物中稍有聚集。复合材料的DMA结果如图8所示，其储能模量增加约300％。 The thermogravimetric curves of mEGIC and EGIC in this embodiment are shown in Fig. 1. The TEM results of the composites are shown in Figure 4. It can be seen that graphene is slightly aggregated in the composite. The DMA results for the composite are shown in Figure 8, and the storage modulus is increased by about 300%.
实施例6：复合材料6Example 6: Composite 6
1)将2g膨胀石墨、300mL浓硫酸、50mL浓硝酸混合后加入到500mL三口烧瓶中，在55℃下反应1小时，得到低氧化程度的膨胀石墨(EGIC)。1) 2 g of expanded graphite, 300 mL of concentrated sulfuric acid, and 50 mL of concentrated nitric acid were mixed, and then added to a 500 mL three-necked flask, and reacted at 55 ° C for 1 hour to obtain expanded graphite (EGIC) having a low degree of oxidation.
2)将上述EGIC加入到含有50mL去离子水和100mL乙醇的混合溶剂的三口烧瓶中，在62℃下搅拌。然后将5mL硅烷偶联剂(乙烯基三乙氧基硅烷)加入到pH＝5的80mL去离子水中搅拌水解，待硅烷偶联剂水解完后加入到上述EGIC的混合溶液中在62℃下继续反应2h。产物用100mL和200mL去离子水洗涤后，抽滤得到改性后的mEGIC。2) The above EGIC was placed in a three-necked flask containing a mixed solvent of 50 mL of deionized water and 100 mL of ethanol, and stirred at 62 °C. Then, 5 mL of a silane coupling agent (vinyltriethoxysilane) was added to 80 mL of deionized water at pH=5 to stir and hydrolyze. After the hydrolysis of the silane coupling agent was completed, it was added to the mixed solution of the above EGIC and continued at 62 ° C. Reaction 2h. The product was washed with 100 mL and 200 mL of deionized water, and filtered to give a modified mEGIC.
3)将1.5g上述mEGIC、30g MMA、0.15g BPO加入含有100mL NMP溶剂的500mL三口烧瓶中，在常温和氮气保护下搅拌6h，然后升温至80℃反应7h后结束反应。接着，将产物倒入500mL甲醇中，有黑色固体颗粒产生。离心分离，留取下层沉淀，用乙醇和水洗涤多次后将产物于80℃鼓风烘箱中干燥24小时，得到黑色粉末状固体，即为目标产物硅烷化石墨烯改性的PMMA复合材料。石墨烯在复合材料中的含量为10wt％。3) 1.5 g of the above mEGIC, 30 g of MMA, and 0.15 g of BPO were placed in a 500 mL three-necked flask containing 100 mL of NMP solvent, stirred at room temperature under nitrogen for 6 h, and then heated to 80 ° C for 7 h to terminate the reaction. Next, the product was poured into 500 mL of methanol, and black solid particles were produced. The mixture was centrifuged, and the lower layer precipitate was taken. After washing a plurality of times with ethanol and water, the product was dried in a blast oven at 80 ° C for 24 hours to obtain a black powdery solid, which was a target product silylated graphene-modified PMMA composite. The content of graphene in the composite was 10% by weight.
本实施例所制得复合材料结构和性能与实施例5相当。The structure and properties of the composite material produced in this example were comparable to those of Example 5.
对比例1：复合材料C1Comparative Example 1: Composite C1
同实施例1，不同之处在于，不添加硅烷偶联剂MPS，具体步骤包括：The same as in the first embodiment, except that the silane coupling agent MPS is not added, and the specific steps include:
将2g膨胀石墨、350mL浓硫酸、2g高锰酸钾混合后加入到500mL三口烧瓶中，在35℃下反应1小时，得到低氧化程度的膨胀石墨(EGIC)。2 g of expanded graphite, 350 mL of concentrated sulfuric acid, and 2 g of potassium permanganate were mixed, and the mixture was placed in a 500 mL three-necked flask, and reacted at 35 ° C for 1 hour to obtain expanded graphite (EGIC) having a low degree of oxidation.
将0.5g上述未经修饰的EGIC、30g MMA、0.15g BPO加入到含有100mL NMP溶剂的500mL三口烧瓶中，在常温和氮气保护下搅拌4h，然后升温至80℃反应7h后结束反应。随后将产物倒入500mL甲醇中，有黑色固体颗粒产生。离心分离，留取下层沉淀，用乙醇和水洗涤多次后，将产物于80℃鼓风烘箱中干燥24小时，得到黑色粉末状固体，即为石墨烯改性的PMMA复合材料C1，其中，石墨烯的含量为1wt％。0.5 g of the above unmodified EGIC, 30 g of MMA, and 0.15 g of BPO were placed in a 500 mL three-necked flask containing 100 mL of NMP solvent, stirred at room temperature under a nitrogen atmosphere for 4 hours, and then heated to 80 ° C for 7 hours to complete the reaction. The product was then poured into 500 mL of methanol with black solid particles. After centrifuging, the lower layer precipitate is taken, and after washing with ethanol and water for a plurality of times, the product is dried in a blast oven at 80 ° C for 24 hours to obtain a black powdery solid, which is a graphene-modified PMMA composite material C1, wherein The content of graphene was 1% by weight.
本对比例中，mEGIC与EGIC的热失重曲线也基本如图1所示。复合材料C1的透射电子显微镜结果如图5所示，可以看出石墨烯在复合材料C1中的分散明显不如mEGIC改性后的复合材料1(图2)。In this comparison example, the thermogravimetric curves of mEGIC and EGIC are also basically shown in Figure 1. The results of transmission electron microscopy of composite C1 are shown in Fig. 5. It can be seen that the dispersion of graphene in composite C1 is not as good as that of composite 1 after mEGIC modification (Fig. 2).
可以看出，未经硅烷偶联剂修饰的EGIC不利于MMA进入EGIC层间反应，因而无法很好地实现石墨烯的剥离。It can be seen that the EGIC modified without the silane coupling agent is not conducive to the entry of the MMA into the EGIC interlayer reaction, and thus the peeling of the graphene is not well achieved.
复合材料C1的DMA结果如图9(1wt％EGIC曲线)所示，可以看到复合物储能模量未发生明显改变。 The DMA results for composite C1 are shown in Figure 9 (1 wt% EGIC curve) and it can be seen that the storage modulus of the composite did not change significantly.
对比例2：复合材料C2Comparative Example 2: Composite C2
同实施例3，不同之处在于，不添加硅烷偶联剂MPS，具体步骤包括：The same as in the third embodiment, except that the silane coupling agent MPS is not added, and the specific steps include:
1)将1g膨胀石墨、200mL浓硫酸、1g高锰酸钾混合后加入到500mL三口烧瓶中，在35℃下反应1小时，得到轻度氧化的膨胀石墨(EGIC)。1) 1 g of expanded graphite, 200 mL of concentrated sulfuric acid, and 1 g of potassium permanganate were mixed, and then added to a 500 mL three-necked flask, and reacted at 35 ° C for 1 hour to obtain slightly oxidized expanded graphite (EGIC).
2)将1g上述未经修饰的EGIC、30g MMA、0.15g BPO加入含有100mL NMP溶剂的500mL三口烧瓶中，在常温和氮气保护下搅拌5h，然后升温至80℃反应7h后结束反应。随后，将产物倒入500mL甲醇中，有黑色固体颗粒产生。离心分离，留取下层沉淀，用乙醇和水洗涤多次后将产物于80℃鼓风烘箱中干燥24小时，得到黑色粉末状固体，即为目标产物石墨烯改性的PMMA复合材料，其中，石墨烯的含量为4wt％。2) 1 g of the above unmodified EGIC, 30 g of MMA, and 0.15 g of BPO were placed in a 500 mL three-necked flask containing 100 mL of NMP solvent, stirred at room temperature under a nitrogen atmosphere for 5 hours, and then heated to 80 ° C for 7 hours to complete the reaction. Subsequently, the product was poured into 500 mL of methanol, and black solid particles were produced. The mixture is centrifuged, and the lower layer is precipitated. After washing with ethanol and water for several times, the product is dried in a blast oven at 80 ° C for 24 hours to obtain a black powdery solid, which is a target product graphene-modified PMMA composite material, wherein The content of graphene was 4% by weight.
本对比例中，mEGIC与EGIC的热失重曲线基本如图1所示。PMMA复合材料的透射电子显微镜结果如图6所示，可以看出石墨烯在复合材料C2中的分散明显不如mEGIC改性后的复合材料。In this comparative example, the thermogravimetric curves of mEGIC and EGIC are basically as shown in Fig. 1. The results of transmission electron microscopy of PMMA composites are shown in Fig. 6. It can be seen that the dispersion of graphene in composite C2 is not as good as that of mEGIC modified composites.
可以看出，未经硅烷偶联剂修饰的EGIC不利于MMA进入EGIC层间反应，因而无法实现对EGIC的充分剥离。It can be seen that EGIC modified without a silane coupling agent is not conducive to the entry of MMA into the EGIC interlayer reaction, and thus sufficient peeling of EGIC cannot be achieved.
复合材料C2的DMA数据如图9(4wt％EGIC曲线)所示，可以看到复合物储能模量增加约58％，明显低于复合材料3所增加的储能模量。The DMA data of composite C2 is shown in Figure 9 (4 wt% EGIC curve), and it can be seen that the composite storage modulus increases by about 58%, which is significantly lower than the increased storage modulus of composite 3.
对比例3：复合材料C3Comparative Example 3: Composite C3
同实施例5，不同之处在于，不添加硅烷偶联剂MPS，具体步骤包括：The same as the embodiment 5, except that the silane coupling agent MPS is not added, and the specific steps include:
1)将2g膨胀石墨、350mL浓硫酸、2g高锰酸钾混合后加入到500mL三口烧瓶中，在35℃下反应1小时，得到轻度氧化的膨胀石墨(EGIC)。1) 2 g of expanded graphite, 350 mL of concentrated sulfuric acid, and 2 g of potassium permanganate were mixed, and then added to a 500 mL three-necked flask, and reacted at 35 ° C for 1 hour to obtain slightly oxidized expanded graphite (EGIC).
2)将1.5g上述未经修饰的EGIC、30g MMA、0.15g BPO加入含有100mL NMP溶剂的500mL三口烧瓶中，在常温和氮气保护下搅拌6h，然后升温至80℃反应7h后结束反应。随后，将产物倒入500mL甲醇中，有黑色固体颗粒产生。离心分离，留取下层沉淀，用乙醇和水洗涤多次后将产物于80℃鼓风烘箱中干燥24小时，得到黑色粉末状固体，即为目标产物石墨烯改性的PMMA复合材料，其中，石墨烯的含量为10wt％。2) 1.5 g of the above unmodified EGIC, 30 g of MMA, and 0.15 g of BPO were placed in a 500 mL three-necked flask containing 100 mL of NMP solvent, stirred at room temperature under nitrogen for 6 h, and then heated to 80 ° C for 7 h to terminate the reaction. Subsequently, the product was poured into 500 mL of methanol, and black solid particles were produced. The mixture is centrifuged, and the lower layer is precipitated. After washing with ethanol and water for several times, the product is dried in a blast oven at 80 ° C for 24 hours to obtain a black powdery solid, which is a target product graphene-modified PMMA composite material, wherein The content of graphene was 10% by weight.
本对比例中，mEGIC与EGIC的热失重曲线基本如图1所示。PMMA复合材料的透射电子显微镜结果如图7所示，可以看出石墨烯在复合材料C3中的分散明显不如mEGIC改性后的复合材料。In this comparative example, the thermogravimetric curves of mEGIC and EGIC are basically as shown in Fig. 1. The results of transmission electron microscopy of PMMA composites are shown in Fig. 7. It can be seen that the dispersion of graphene in composite C3 is not as good as that of mEGIC modified composites.
可以看出，未经硅烷偶联剂修饰的EGIC不利于MMA进入EGIC层间反应，因而不能 对EGIC的产生充分剥离效果。It can be seen that EGIC not modified by silane coupling agent is not conducive to MMA entering the EGIC interlayer reaction, and thus cannot The EGIC produces a sufficient peeling effect.
复合材料C3的DMA数据如图9(10wt％EGIC曲线)所示，可以看到复合物储能模量增加108％，大大低于复合材料5所增加的储能模量。The DMA data of composite C3 is shown in Figure 9 (10 wt% EGIC curve), and it can be seen that the storage modulus of the composite increases by 108%, which is much lower than the increased storage modulus of composite 5.
在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。 All documents mentioned in the present application are hereby incorporated by reference in their entirety in their entireties in the the the the the the the the In addition, it should be understood that various modifications and changes may be made by those skilled in the art in the form of the appended claims.

Claims (6)

  1. 一种超高电导率石墨烯改性聚甲基丙烯酸甲酯(PMMA)复合物的制备方法，其特征在于，包括步骤：A preparation method of ultra-high conductivity graphene modified polymethyl methacrylate (PMMA) composite, characterized in that the method comprises the steps of:
    (1)将1～3g膨胀石墨用200～600mL浓硫酸和氧化剂轻微氧化；(1) 1 to 3 g of expanded graphite is slightly oxidized with 200 to 600 mL of concentrated sulfuric acid and an oxidizing agent;
    (2)将轻微氧化后的膨胀石墨(EGIC)加入到50～150mL去离子水和100～300mL乙醇组成的混合溶液中，在60～70℃下搅拌均匀，得到EGIC的混合溶液；将2.5～7.5mL的硅烷偶联剂在pH＝4～5的40～120mL的水溶液中搅拌水解，然后将彻底水解后的硅烷偶联剂溶液倒入所述EGIC的混合溶液中在60～70℃下继续反应2小时，将产物用甲醇和水洗涤抽滤，得到硅氧烷改性的膨胀石墨(mEGIC)；(2) Add the slightly oxidized expanded graphite (EGIC) to a mixed solution of 50-150 mL of deionized water and 100-300 mL of ethanol, and stir uniformly at 60-70 ° C to obtain a mixed solution of EGIC; 7.5 mL of the silane coupling agent is stirred and hydrolyzed in an aqueous solution of 40 to 120 mL of pH=4 to 5, and then the thoroughly hydrolyzed silane coupling agent solution is poured into the mixed solution of the EGIC to continue at 60 to 70 °C. After reacting for 2 hours, the product was washed with methanol and water to obtain a siloxane-modified expanded graphite (mEGIC);
    (3)将步骤(2)得到的mEGIC、甲基丙烯酸甲酯(MMA)和过氧化二苯甲酰(BPO)加入到N-甲基吡咯烷酮(NMP)溶剂中，并于常温下搅拌一段时间，升温到70～90℃后反应7～12小时，将产物倒入到甲醇中进行离心、洗涤和真空干燥处理，得到改性的PMMA复合物；在所得PMMA复合物中，mEGIC占整个PMMA复合物的质量分数为1％～10％，甲基丙烯酸甲酯和过氧化二苯甲酰质量比为100～300：1。(3) adding mEGIC, methyl methacrylate (MMA) and dibenzoyl peroxide (BPO) obtained in the step (2) to a solvent of N-methylpyrrolidone (NMP), and stirring at room temperature for a while. After heating to 70-90 ° C for 7-12 hours, the product is poured into methanol for centrifugation, washing and vacuum drying to obtain a modified PMMA composite; in the obtained PMMA composite, mEGIC accounts for the entire PMMA composite. The mass fraction of the substance is 1% to 10%, and the mass ratio of methyl methacrylate to dibenzoyl peroxide is 100 to 300:1.
  2. 根据权利要求1所述的方法，其特征在于步骤(1)中所述膨胀石墨为热膨胀石墨或化学膨胀石墨。The method according to claim 1, wherein said expanded graphite in step (1) is thermally expanded graphite or chemically expanded graphite.
  3. 根据权利要求1所述的方法，其特征在于步骤(1)中所用氧化剂为高锰酸钾、重铬酸钾、体积比为1:1的浓硫酸/浓硝酸混合物或高铁酸钾中任一种，氧化剂与原料膨胀石墨质量比为(1-5)：1。The method according to claim 1, wherein the oxidizing agent used in the step (1) is potassium permanganate, potassium dichromate, a concentrated sulfuric acid/concentrated nitric acid mixture having a volume ratio of 1:1 or potassium ferrate. The mass ratio of the oxidant to the expanded graphite of the raw material is (1-5):1.
  4. 根据权利要求1所述的方法，其特征在于步骤(2)中所用硅烷偶联剂为3-(甲基丙烯酰氧)丙基三甲氧基硅烷(MPS)、乙烯基三甲氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷或乙烯基三乙氧基硅烷中任一种。The method according to claim 1, wherein the silane coupling agent used in the step (2) is 3-(methacryloyloxy)propyltrimethoxysilane (MPS), vinyltrimethoxysilane, ethylene. Any of tris(2-methoxyethoxy)silane or vinyltriethoxysilane.
  5. 根据权利要求1所述的方法，其特征在于步骤(2)中所用硅烷偶联剂溶液的浓度为0.02～0.2g/mL。The method according to claim 1, wherein the concentration of the silane coupling agent solution used in the step (2) is 0.02 to 0.2 g/mL.
  6. 根据权利要求1所述的方法，其特征在于步骤(3)中常温下搅拌一段时间为在常温下搅拌0.5～6小时。 The method according to claim 1, wherein the step (3) is stirred at a normal temperature for a period of time at a normal temperature for 0.5 to 6 hours.
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CN116519493B (en) * 2023-05-06 2024-01-19 天津大学 High-temperature creep vacuum/atmosphere environment device
CN116519493A (en) * 2023-05-06 2023-08-01 天津大学 High-temperature creep vacuum/atmosphere environment device
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