CN117963895A - Xanthan gum edge grafting modified graphene and aqueous dispersion thereof and preparation method - Google Patents
Xanthan gum edge grafting modified graphene and aqueous dispersion thereof and preparation method Download PDFInfo
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- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
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Abstract
本发明属于石墨烯制备技术领域,涉及一种黄原胶边缘接枝改性石墨烯及其水分散液和制备方法。所述黄原胶边缘接枝改性石墨烯包括石墨烯和接枝在其边缘上的黄原胶,以边缘接枝改性石墨烯的总质量计,所述黄原胶边缘接枝改性石墨烯中接枝的黄原胶的质量含量为1‑6%。黄原胶能够提高溶液粘度,将磨盘间剪切力间接传递给石墨片,进一步降低对石墨晶格的破坏,并提高了石墨片的剥离效果。
The invention belongs to the technical field of graphene preparation, and relates to a xanthan gum edge-grafted modified graphene, an aqueous dispersion thereof, and a preparation method thereof. The xanthan gum edge-grafted modified graphene comprises graphene and xanthan gum grafted on its edge, and the mass content of the grafted xanthan gum in the xanthan gum edge-grafted modified graphene is 1-6% based on the total mass of the edge-grafted modified graphene. The xanthan gum can increase the viscosity of the solution, indirectly transmit the shear force between the grinding discs to the graphite sheet, further reduce the damage to the graphite lattice, and improve the peeling effect of the graphite sheet.
Description
技术领域Technical Field
本发明属于石墨烯制备技术领域,具体地,涉及一种黄原胶边缘接枝改性石墨烯、一种黄原胶边缘接枝改性石墨烯的水分散液,以及它们的制备方法。The invention belongs to the technical field of graphene preparation, and specifically relates to xanthan gum edge-grafted modified graphene, an aqueous dispersion of xanthan gum edge-grafted modified graphene, and preparation methods thereof.
背景技术Background technique
石墨烯是由一个碳原子与周围三个紧邻碳原子结合形成的蜂窝状结构的碳原子单层。石墨烯作为一种新型材料,以其高透光、高导电、高导热、高比表面积,以及优异的力学性能而备受瞩目。目前,石墨烯处于大规模制备和应用的探索阶段。高质量低成本功能化石墨烯的制备技术是未来规模应用的基础。科技人员已经开发了一系列制备技术:机械剥离法、氧化还原法、化学气相沉积法、外延生长法、热膨胀法和电化学法等。其中,机械剥离法和氧化还原法都是基于石墨原料通过机械或化学剥离技术制备,原料来源丰富,易于控制成本,更适合石墨烯的规模化生产。氧化还原法通过强氧化剂将天然石墨氧化,表面引入丰富极性基团,通过溶剂化作用或超声分散作用得到氧化石墨烯后,再还原去除氧化石墨烯表面的极性基团,得到石墨烯。但是,在生产过程中用到大量强酸和强氧化剂,例如浓硫酸、发烟硝酸、高锰酸钾、高氯酸等,带来严重废液污染。制备的石墨烯存在一定的缺陷,例如还原作用除去的极性基团留下的五元环、七元环等拓扑缺陷或存在羟基基团的结构缺陷,这些将导致石墨烯部分性能的损失,使石墨烯的应用受到限制。国家标准GB/T30544.13-2018:《纳米科技术语第13部分:石墨烯及相关二维材料》中,单独定义了氧化石墨烯和还原氧化石墨烯,以与石墨烯区分。Graphene is a single layer of carbon atoms with a honeycomb structure formed by a carbon atom and three adjacent carbon atoms. As a new type of material, graphene has attracted much attention for its high light transmittance, high electrical conductivity, high thermal conductivity, high specific surface area, and excellent mechanical properties. At present, graphene is in the exploratory stage of large-scale preparation and application. The preparation technology of high-quality and low-cost functionalized graphene is the basis for future large-scale application. Scientific and technological personnel have developed a series of preparation technologies: mechanical exfoliation, redox method, chemical vapor deposition method, epitaxial growth method, thermal expansion method and electrochemical method. Among them, mechanical exfoliation and redox method are both based on the preparation of graphite raw materials through mechanical or chemical exfoliation technology. The raw material source is abundant, the cost is easy to control, and it is more suitable for large-scale production of graphene. The redox method oxidizes natural graphite with a strong oxidant, introduces rich polar groups on the surface, obtains graphene oxide through solvation or ultrasonic dispersion, and then reduces and removes the polar groups on the surface of graphene oxide to obtain graphene. However, a large amount of strong acid and strong oxidant is used in the production process, such as concentrated sulfuric acid, fuming nitric acid, potassium permanganate, perchloric acid, etc., which brings serious waste liquid pollution. The prepared graphene has certain defects, such as topological defects such as five-membered rings and seven-membered rings left by the polar groups removed by reduction or structural defects of hydroxyl groups, which will lead to the loss of some properties of graphene and limit the application of graphene. In the national standard GB/T30544.13-2018: "Nanotechnology Terminology Part 13: Graphene and Related Two-Dimensional Materials", graphene oxide and reduced graphene oxide are separately defined to distinguish them from graphene.
经过氧化得到的石墨烯表面含有丰富的含氧基团,如环氧基、羟基和羧基等,可以通过化学反应对其进行化学改性。Salavagione H J等人(Salavagione H J,G Martínez,MA Gómez.Synthesis of poly(vinyl alcohol)/reduced graphite oxidenanocomposites with improved thermal and electrical properties[J].Journal ofMaterials Chemistry,2009,19(28):5027-5032.)通过聚乙烯醇(PVA)上的羟基与氧化石墨烯上的羧基之间的酯化反应将PVA接枝到氧化石墨烯上,得到PVA接枝氧化石墨烯。徐国强等人(徐国强,徐鹏武,施冬健,等.PEG接枝氧化石墨烯的制备与细胞成像[J].无机化学学报,2014,30(009):1994-1999.)研究了聚环氧乙烷接枝氧化石墨烯。李善荣等人(李善荣,陆绍荣,祁博,等.联苯型热致性液晶接枝氧化石墨烯的合成及应用[J].高分子材料科学与工程,2013,29(007):17-20)研究了联苯型热致性液晶接枝氧化石墨烯。他们都是利用氧化法制备的氧化石墨烯表面丰富活性基团制备接枝氧化石墨烯。孙爽等人(孙爽,马骁飞,王楠,等.GN-PVA/PVA复合膜材料的制备及性能测试[J].化学与生物工程,2016,33(9):5.)通过PVA与氧化石墨烯反应,再还原制备了PVA接枝还原氧化石墨烯。目前,聚合物接枝石墨烯主要基于以上方法制备。但是,基于氧化石墨烯的接枝再还原的方法制备的聚合物接枝石墨烯表面五元环、七元环等拓扑缺陷和残留含氧基团仍存在,属于聚合物接枝氧化石墨烯或聚合物接枝还原氧化石墨烯,其结构不同于聚合物接枝石墨烯。The surface of graphene obtained by oxidation contains abundant oxygen-containing groups, such as epoxy, hydroxyl and carboxyl groups, which can be chemically modified by chemical reactions. Salavagione HJ et al. (Salavagione HJ, G Martínez, MA Gómez. Synthesis of poly(vinyl alcohol)/reduced graphite oxide nanocomposites with improved thermal and electrical properties [J]. Journal of Materials Chemistry, 2009, 19 (28): 5027-5032.) grafted PVA onto graphene oxide through esterification reaction between hydroxyl groups on PVA and carboxyl groups on graphene oxide to obtain PVA-grafted graphene oxide. Xu Guoqiang et al. (Xu Guoqiang, Xu Pengwu, Shi Dongjian, et al. Preparation and Cell Imaging of PEG-grafted Graphene Oxide [J]. Journal of Inorganic Chemistry, 2014, 30 (009): 1994-1999.) studied polyethylene oxide grafted graphene oxide. Li Shanrong et al. (Li Shanrong, Lu Shaorong, Qi Bo, et al. Synthesis and application of biphenyl-type thermotropic liquid crystal grafted graphene oxide [J]. Polymer Materials Science and Engineering, 2013, 29 (007): 17-20) studied biphenyl-type thermotropic liquid crystal grafted graphene oxide. They all used the rich active groups on the surface of graphene oxide prepared by oxidation to prepare grafted graphene oxide. Sun Shuang et al. (Sun Shuang, Ma Xiaofei, Wang Nan, et al. Preparation and performance test of GN-PVA/PVA composite film materials [J]. Chemistry and Bioengineering, 2016, 33 (9): 5.) prepared PVA grafted reduced graphene oxide by reacting PVA with graphene oxide and then reducing it. At present, polymer grafted graphene is mainly prepared based on the above methods. However, the topological defects such as five-membered rings and seven-membered rings and residual oxygen-containing groups on the surface of the polymer-grafted graphene prepared by the method of grafting and reducing graphene oxide still exist, which belongs to polymer-grafted graphene oxide or polymer-grafted reduced graphene oxide, and its structure is different from that of polymer-grafted graphene.
常用的机械剥离方法有球磨法、砂磨法、超声法等。这些方法虽然能够规模化生产石墨烯,但是因为机械力的破坏作用大,石墨烯的结构破坏严重,尺寸也往往较小,甚至小于100纳米。因此机械剥离法的技术关键是降低破坏性,制备较大面积的石墨烯。Commonly used mechanical exfoliation methods include ball milling, sand milling, and ultrasonic methods. Although these methods can produce graphene on a large scale, due to the large destructive effect of mechanical force, the structure of graphene is severely damaged and the size is often small, even less than 100 nanometers. Therefore, the technical key to mechanical exfoliation is to reduce destructiveness and prepare graphene with a larger area.
发明内容Summary of the invention
本发明的目的是提供一种黄原胶边缘接枝改性石墨烯,稳定的黄原胶边缘接枝改性石墨烯的水分散液以及它们的制备方法。The invention aims to provide a xanthan gum edge-grafted modified graphene, a stable aqueous dispersion of the xanthan gum edge-grafted modified graphene and a preparation method thereof.
本发明的第一方面提供一种黄原胶边缘接枝改性石墨烯,所述黄原胶边缘接枝改性石墨烯包括石墨烯和接枝在其边缘上的黄原胶,以边缘接枝改性石墨烯的总质量计,所述黄原胶边缘接枝改性石墨烯中接枝的黄原胶的质量含量为1-6%,优选1-5%。The first aspect of the present invention provides a xanthan gum edge-grafted modified graphene, wherein the xanthan gum edge-grafted modified graphene comprises graphene and xanthan gum grafted on its edge, and the mass content of the grafted xanthan gum in the xanthan gum edge-grafted modified graphene is 1-6%, preferably 1-5%, based on the total mass of the edge-grafted modified graphene.
本发明的第二方面提供一种黄原胶边缘接枝改性石墨烯的水分散液,所述水分散液包括水和稳定分散其中的黄原胶边缘接枝改性石墨烯,所述黄原胶边缘接枝改性石墨烯为上述的黄原胶边缘接枝改性石墨烯。The second aspect of the present invention provides an aqueous dispersion of xanthan gum edge-grafted modified graphene, the aqueous dispersion comprising water and xanthan gum edge-grafted modified graphene stably dispersed therein, and the xanthan gum edge-grafted modified graphene is the above-mentioned xanthan gum edge-grafted modified graphene.
本发明的第三方面提供上述黄原胶边缘接枝改性石墨烯的水分散液的制备方法,包括以下步骤:The third aspect of the present invention provides a method for preparing the aqueous dispersion of the above-mentioned xanthan gum edge-grafted modified graphene, comprising the following steps:
将黄原胶、水、石墨混合均匀,在磨盘釜中进行研磨,研磨结束后静置并去除沉淀,得到所述黄原胶边缘接枝改性石墨烯的水分散液。The xanthan gum, water and graphite are uniformly mixed and ground in a grinding wheel kettle. After the grinding, the mixture is allowed to stand and the precipitate is removed to obtain an aqueous dispersion of the xanthan gum edge-grafted modified graphene.
本发明的第四方面提供上述黄原胶边缘接枝改性石墨烯的制备方法,包括以下步骤:The fourth aspect of the present invention provides a method for preparing the above-mentioned xanthan gum edge-grafted modified graphene, comprising the following steps:
(1)按照上述方法制得黄原胶边缘接枝改性石墨烯的水分散液;(1) preparing an aqueous dispersion of xanthan gum edge-grafted modified graphene according to the above method;
(2)将步骤(1)得到的黄原胶边缘接枝改性石墨烯的水分散液进行过滤、烘干,得到所述黄原胶边缘接枝改性石墨烯。(2) filtering and drying the aqueous dispersion of the xanthan gum edge-grafted modified graphene obtained in step (1) to obtain the xanthan gum edge-grafted modified graphene.
采用上述技术发明制备的黄原胶接枝石墨烯的水分散液具有如下优点:The aqueous dispersion of xanthan gum grafted graphene prepared by the above technical invention has the following advantages:
1、相较于超声、球磨、砂磨等研磨工艺,磨盘对石墨晶体结构的破坏作用弱,易于制备较大片层的黄原胶边缘接枝石墨烯。1. Compared with ultrasonic, ball milling, sand milling and other grinding processes, the grinding disc has a weaker destructive effect on the graphite crystal structure, and it is easy to prepare larger sheets of xanthan gum edge-grafted graphene.
2、黄原胶能够提高溶液粘度,将磨盘间剪切力间接传递给石墨片,进一步降低对石墨晶格的破坏,并提高了石墨片的剥离效果。2. Xanthan gum can increase the viscosity of the solution and indirectly transfer the shear force between the grinding discs to the graphite flakes, further reducing the damage to the graphite lattice and improving the peeling effect of the graphite flakes.
3、在剥离过程中,黄原胶接枝到石墨烯的边缘,并使黄原胶边缘接枝石墨烯在水中稳定分散。3. During the stripping process, xanthan gum is grafted to the edge of graphene, and the xanthan gum edge-grafted graphene is stably dispersed in water.
4、制备过程中,黄原胶边缘接枝石墨烯能够稳定分散在水中,而石墨片会沉淀出来,因此容易进行分离。4. During the preparation process, xanthan gum edge-grafted graphene can be stably dispersed in water, while graphite sheets will precipitate out, so it is easy to separate.
本发明的其它特征和优点将在随后具体实施方式部分予以详细说明。Other features and advantages of the present invention will be described in detail in the following detailed description.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
通过结合附图对本发明示例性实施方式进行更详细的描述。Exemplary embodiments of the present invention will be described in more detail with reference to the accompanying drawings.
图1为本发明一种实施方式中接枝石墨烯水分散液的制备装置示意图;FIG1 is a schematic diagram of a device for preparing a grafted graphene aqueous dispersion in one embodiment of the present invention;
图2为实施例1-5制备的黄原胶边缘接枝石墨烯的稳定水分散液的照片;FIG2 is a photograph of a stable aqueous dispersion of xanthan gum edge-grafted graphene prepared in Examples 1-5;
图3为实施例1制备的黄原胶边缘接枝石墨烯的扫描电子显微镜照片;FIG3 is a scanning electron microscope photograph of xanthan gum edge-grafted graphene prepared in Example 1;
图4为实施例1制备的黄原胶边缘接枝石墨烯的透射电子显微镜照片;FIG4 is a transmission electron microscope photograph of xanthan gum edge-grafted graphene prepared in Example 1;
图5为实施例1制备的黄原胶边缘接枝石墨烯的红外吸收光谱图;FIG5 is an infrared absorption spectrum of xanthan gum edge-grafted graphene prepared in Example 1;
图6为对图5红外吸收光谱图的基线拉平进行处理后的谱图;FIG6 is a spectrum diagram of the infrared absorption spectrum diagram of FIG5 after baseline flattening;
图7为实施例1制备的黄原胶边缘接枝石墨烯的热重分析图,上方曲线代表鳞片石墨,下方曲线代表黄原胶边缘接枝石墨烯。Figure 7 is a thermogravimetric analysis graph of xanthan gum edge-grafted graphene prepared in Example 1, the upper curve represents flake graphite, and the lower curve represents xanthan gum edge-grafted graphene.
具体实施方式Detailed ways
以下对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.
本发明提供一种黄原胶边缘接枝改性石墨烯,所述黄原胶边缘接枝改性石墨烯包括石墨烯和接枝在其边缘上的黄原胶,以边缘接枝改性石墨烯的总质量计,所述黄原胶边缘接枝改性石墨烯中接枝的黄原胶的质量含量为1-6%,优选1-5%,例如1%、2%、3%、4%、5%。The invention provides a xanthan gum edge-grafted modified graphene, which comprises graphene and xanthan gum grafted on the edge thereof. Based on the total mass of the edge-grafted modified graphene, the mass content of the grafted xanthan gum in the xanthan gum edge-grafted modified graphene is 1-6%, preferably 1-5%, for example 1%, 2%, 3%, 4%, 5%.
本发明中,所述边缘接枝改性石墨烯中接枝的黄原胶部分的质量含量可通过热重分析方法测得。例如,在样品氮气流速20.0ml/min,平衡氮气流速40.0ml/min的条件下,从50.00℃以20.00℃/min的升温速度至800.00℃测量黄原胶边缘接枝石墨烯样品的失质量即是接枝到石墨烯的黄原胶高分子的质量含量。In the present invention, the mass content of the grafted xanthan gum portion in the edge-grafted modified graphene can be measured by thermogravimetric analysis. For example, under the conditions of a sample nitrogen flow rate of 20.0 ml/min and a balance nitrogen flow rate of 40.0 ml/min, the mass loss of the xanthan gum edge-grafted graphene sample is measured from 50.00°C to 800.00°C at a heating rate of 20.00°C/min, which is the mass content of the xanthan gum polymer grafted to the graphene.
本发明中,“黄原胶”既可指化合物形态,也可以指基团形态,例如“黄原胶边缘接枝改性石墨烯”中的黄原胶是基团形态,制备方法中黄原胶是化合物形态。本领域技术人员能够根据不同语境明确区分所指含义。In the present invention, "xanthan gum" can refer to either a compound form or a group form. For example, the xanthan gum in "xanthan gum edge-grafted modified graphene" is a group form, and the xanthan gum in the preparation method is a compound form. Those skilled in the art can clearly distinguish the meaning according to different contexts.
本发明人在开展磨盘剥离石墨/水浆液制备石墨烯的研究过程中发现,向体系中加入黄原胶增加体系粘度可提高石墨剥离效果,并且,出人意料的是,即使在水溶液中,黄原胶也能够接枝到剥离的石墨烯边缘上,从而形成稳定的黄原胶接枝改性石墨烯的水分散液。The inventors discovered during their research on preparing graphene by disc exfoliating graphite/water slurry that adding xanthan gum to the system to increase the viscosity of the system can improve the graphite exfoliation effect, and surprisingly, even in aqueous solution, xanthan gum can be grafted onto the edges of exfoliated graphene, thereby forming a stable aqueous dispersion of xanthan gum-grafted modified graphene.
本发明的黄原胶边缘接枝石墨烯的结构和性质与现有的接枝氧化石墨烯或接枝还原氧化石墨烯存在显著不同。The structure and properties of the xanthan gum edge-grafted graphene of the present invention are significantly different from those of the existing grafted graphene oxide or grafted reduced graphene oxide.
从结构上看,国家标准GB/T30544.13-2018中单独定义了氧化石墨烯和还原氧化石墨烯,氧化石墨烯是对石墨进行氧化及剥离后所得到的化学改性石墨烯,其表面已被强氧化改性,含氧量高;还原氧化石墨烯是氧含量被降低后的氧化石墨烯,实际仍会残留部分含氧功能基团,并且SP3化学键也无法完全还原为SP2化学键,留下很多拓扑缺陷。因此氧化石墨烯和还原氧化石墨烯与石墨烯的结构区别较大。本发明采用的是石墨烯,并非氧化石墨烯和还原氧化石墨烯。从性质上看,文献报道的黄原胶改性石墨烯多是基于氧化石墨烯的含氧基团与黄原胶的接枝反应,然后再还原制备黄原胶接枝石墨烯。Structurally, graphene oxide and reduced graphene oxide are separately defined in the national standard GB/T30544.13-2018. Graphene oxide is a chemically modified graphene obtained by oxidizing and peeling graphite, and its surface has been strongly oxidized and modified, with a high oxygen content; reduced graphene oxide is graphene oxide after the oxygen content is reduced, and some oxygen-containing functional groups will actually remain, and the sp 3 chemical bonds cannot be completely reduced to sp 2 chemical bonds, leaving many topological defects. Therefore, the structures of graphene oxide and reduced graphene oxide are quite different from those of graphene. The present invention uses graphene, not graphene oxide and reduced graphene oxide. In terms of properties, the xanthan gum modified graphene reported in the literature is mostly based on the grafting reaction of oxygen-containing groups of graphene oxide with xanthan gum, and then reduced to prepare xanthan gum grafted graphene.
本发明中选用的黄原胶可以是现有技术可得到的各种类型的能水溶的黄原胶,例如透明型,速溶型或普通型。The xanthan gum used in the present invention can be various types of water-soluble xanthan gum available in the prior art, such as transparent type, instant type or ordinary type.
根据本发明,磨盘剪切剥离作用是通过黄原胶水溶液作用于石墨,对石墨烯的破坏作用相对球磨、砂磨等方法小,因此所述边缘接枝石墨烯片层相对较大,具体地,所述边缘接枝改性石墨烯的平均片径为1-5μm。According to the present invention, the shearing and peeling effect of the grinding disc is achieved by the xanthan gum aqueous solution acting on graphite, and the destructive effect on graphene is relatively small compared with methods such as ball milling and sand milling. Therefore, the edge-grafted graphene flakes are relatively large. Specifically, the average flake diameter of the edge-grafted modified graphene is 1-5 μm.
所述边缘接枝改性石墨烯的平均片径可通过扫描电子显微镜(SEM)或原子力显微镜成像后,随机测量10片以上石墨烯的尺寸计算平均值得到。单片石墨烯尺寸的测量方法:在石墨烯片层表面尽量通过片层中心划三条线,线与线之间夹角约60°,在三条线上测量石墨烯的长度,计算平均值作为此片石墨烯的尺寸。The average sheet diameter of the edge-grafted modified graphene can be obtained by randomly measuring the sizes of more than 10 graphene sheets after imaging by scanning electron microscope (SEM) or atomic force microscope and calculating the average value. The method for measuring the size of a single graphene sheet is as follows: draw three lines on the surface of the graphene sheet through the center of the sheet as much as possible, with the angle between the lines being about 60°, measure the length of the graphene on the three lines, and calculate the average value as the size of the graphene sheet.
本发明还提供一种黄原胶边缘接枝改性石墨烯的水分散液,所述水分散液包括水和稳定分散其中的黄原胶边缘接枝改性石墨烯,所述黄原胶边缘接枝改性石墨烯为上述的黄原胶边缘接枝改性石墨烯。The present invention also provides an aqueous dispersion of xanthan gum edge-grafted modified graphene, which comprises water and xanthan gum edge-grafted modified graphene stably dispersed therein, and the xanthan gum edge-grafted modified graphene is the above-mentioned xanthan gum edge-grafted modified graphene.
根据本发明一种优选实施方式,所述分散液中边缘接枝改性石墨烯的质量分数为1-20%,优选1-15%。例如2%、3%、4%、5%、6%、7%、8%、9%、10%、12%、14%。According to a preferred embodiment of the present invention, the mass fraction of edge-grafted modified graphene in the dispersion is 1-20%, preferably 1-15%, for example 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 14%.
本发明的所述水分散液在室温常压条件下能够稳定超过10个月。所述稳定的时间是指在该时间段内,未发生肉眼可见的沉淀,具体地,沉淀量低于1%。The aqueous dispersion of the present invention can be stable for more than 10 months at room temperature and pressure. The stable time means that no visible precipitation occurs during this period of time, specifically, the amount of precipitation is less than 1%.
本发明还提供上述黄原胶边缘接枝改性石墨烯的水分散液的制备方法,包括以下步骤:The present invention also provides a method for preparing the aqueous dispersion of the xanthan gum edge-grafted modified graphene, comprising the following steps:
将黄原胶、水、石墨混合均匀,在磨盘釜中进行研磨,研磨结束后静置并去除沉淀,得到所述黄原胶边缘接枝改性石墨烯的水分散液。The xanthan gum, water and graphite are uniformly mixed and ground in a grinding wheel kettle. After the grinding, the mixture is allowed to stand and the precipitate is removed to obtain an aqueous dispersion of the xanthan gum edge-grafted modified graphene.
本发明是基于黄原胶水溶液辅助的磨盘剥离石墨同时原位接枝技术,制备的黄原胶接枝在石墨烯的边缘,并稳定分散在水溶液中。The invention is based on a xanthan gum aqueous solution-assisted grinding disc graphite exfoliation and simultaneous in-situ grafting technology, wherein the prepared xanthan gum is grafted on the edge of graphene and stably dispersed in the aqueous solution.
根据本发明一种优选实施方式,所述研磨采用循环操作,使用的机械剥离设备由磨盘和循环两部分组成,其结构示意图如图1所示。磨盘部分包括动磨盘、定磨盘以及转动装置,循环部分包括循环泵、浆料储罐和搅拌装置。其中磨盘材质可选择金属、陶瓷、玻璃、塑料等,优选金属材质。According to a preferred embodiment of the present invention, the grinding adopts a cyclic operation, and the mechanical stripping equipment used is composed of a grinding disc and a circulation part, and its structural schematic diagram is shown in Figure 1. The grinding disc part includes a moving grinding disc, a fixed grinding disc and a rotating device, and the circulation part includes a circulation pump, a slurry storage tank and a stirring device. The grinding disc material can be selected from metal, ceramic, glass, plastic, etc., preferably metal.
在磨盘剥离过程中,动磨盘/静磨盘通过黄原胶的水溶液将剪切力传递给磨盘间的石墨片。石墨片在剪切应力作用下首先沿磨盘转动方向取向,然后被慢慢剥离成更薄的石墨片,最终剥离成石墨烯。在剥离过程中,产生很多新的边缘,新边缘的碳原子的活性较高,与水溶液中的黄原胶反应生成黄原胶边缘接枝石墨烯。本发明的方法显著降低了对石墨晶格的破坏。黄原胶对分散体系的增粘作用,定磨盘和动磨盘间的剪切力更有效作用于浆料中的石墨片,实现石墨烯的剥离制备。在剥离过程中,黄原胶接枝到石墨烯的边缘,从而使制备石墨烯稳定分散在水中。During the disc stripping process, the moving disc/stationary disc transfers the shear force to the graphite flakes between the discs through the aqueous solution of xanthan gum. Under the action of shear stress, the graphite flakes are first oriented along the rotation direction of the disc, and then slowly stripped into thinner graphite flakes, and finally stripped into graphene. During the stripping process, many new edges are generated, and the carbon atoms at the new edges are highly active, which react with the xanthan gum in the aqueous solution to generate xanthan gum edge-grafted graphene. The method of the present invention significantly reduces the damage to the graphite lattice. The viscosity-increasing effect of xanthan gum on the dispersed system and the shear force between the fixed disc and the moving disc more effectively act on the graphite flakes in the slurry, thereby realizing the stripping preparation of graphene. During the stripping process, xanthan gum is grafted to the edge of graphene, so that the prepared graphene is stably dispersed in water.
本发明的所述研磨可以在封闭或敞开体系中进行,该制备过程可为在室温常压下循环研磨,对体系的气氛没有具体要求。The grinding of the present invention can be carried out in a closed or open system. The preparation process can be cyclic grinding at room temperature and normal pressure, and there is no specific requirement for the atmosphere of the system.
本发明选用的研磨条件:转速10-300转/分钟,优选50-200转/分钟;循环剥离时间5-200小时,优选10-150小时,更优选30-120小时。The grinding conditions selected in the present invention are: a rotation speed of 10-300 rpm, preferably 50-200 rpm; a cycle stripping time of 5-200 hours, preferably 10-150 hours, and more preferably 30-120 hours.
本发明体系中黄原胶有两个作用:(1)增加分散体系的粘度,提高磨盘对石墨片的剥离效果,(2)接枝到石墨烯,使石墨烯稳定分散在水溶液中。The xanthan gum in the system of the present invention has two functions: (1) increasing the viscosity of the dispersion system to improve the peeling effect of the grinding disc on the graphite sheet, and (2) grafting to the graphene to make the graphene stably dispersed in the aqueous solution.
本发明中黄原胶边缘接枝石墨烯的水分散液是通过磨盘机械剥离石墨制备,可选用的石墨可以为天然石墨和/或人造石墨,所述天然石墨选自鳞片石墨、块状石墨、隐晶质石墨中的一种或多种,所述人造石墨选自热裂解石墨、高定向热裂解石墨中的一种或多种;所述石墨优选鳞片石墨;所述石墨的颗粒尺寸可以为5-8000目,优选35-3000目,进一步优选50-1600目,更优选50-300目。The aqueous dispersion of xanthan gum edge-grafted graphene in the present invention is prepared by mechanically exfoliating graphite with a grinding disc, and the graphite that can be selected can be natural graphite and/or artificial graphite, the natural graphite is selected from one or more of flake graphite, block graphite, and cryptocrystalline graphite, and the artificial graphite is selected from one or more of thermal cracking graphite and highly oriented thermal cracking graphite; the graphite is preferably flake graphite; the particle size of the graphite can be 5-8000 mesh, preferably 35-3000 mesh, further preferably 50-1600 mesh, and more preferably 50-300 mesh.
根据本发明一种优选实施方式,先将黄原胶和水混合,再加入石墨,以黄原胶和水的总质量计,所述黄原胶的质量分数为0.1-5%,优选0.2-3%。According to a preferred embodiment of the present invention, xanthan gum and water are first mixed, and then graphite is added. The mass fraction of the xanthan gum is 0.1-5%, preferably 0.2-3%, based on the total mass of the xanthan gum and water.
本发明还提供了所述黄原胶边缘接枝改性石墨烯的制备方法,包括以下步骤:The present invention also provides a method for preparing the xanthan gum edge-grafted modified graphene, comprising the following steps:
(1)按照前述的方法制得黄原胶边缘接枝改性石墨烯的水分散液;(1) preparing an aqueous dispersion of xanthan gum edge-grafted modified graphene according to the aforementioned method;
(2)将步骤(1)得到的黄原胶边缘接枝改性石墨烯的水分散液进行过滤、烘干,得到所述黄原胶边缘接枝改性石墨烯。(2) filtering and drying the aqueous dispersion of the xanthan gum edge-grafted modified graphene obtained in step (1) to obtain the xanthan gum edge-grafted modified graphene.
所述过滤可以采用常规的各种方法,优选地,所述过滤采用微孔过滤膜减压过滤,微孔尺寸在100-1000nm,优选200-800nm。The filtration can be carried out by various conventional methods. Preferably, the filtration is carried out by reduced pressure filtration with a microporous filtration membrane, and the micropore size is 100-1000nm, preferably 200-800nm.
根据本发明一种优选实施方式,所述过滤步骤还包括,过滤前对所述黄原胶边缘接枝改性石墨烯的水分散液进行稀释。According to a preferred embodiment of the present invention, the filtering step further comprises diluting the aqueous dispersion of the xanthan gum edge-grafted modified graphene before filtering.
根据本发明一种优选实施方式,所述过滤步骤还包括,过滤后用(去离子)水滤除游离的溶解在水中的黄原胶,以进一步纯化所述黄原胶边缘接枝改性石墨烯。According to a preferred embodiment of the present invention, the filtration step further comprises filtering out free xanthan gum dissolved in water with (deionized) water after filtration to further purify the xanthan gum edge-grafted modified graphene.
本发明采用磨盘工艺,将黄原胶、石墨和水在磨盘间循环剥离加工,定磨盘和动磨盘间的剪切作用通过高粘度黄原胶溶液传递给石墨片,实现了石墨烯的剥离制备。与球磨、砂磨和超声等方法相比,磨盘工艺有效利用了磨盘间的剥离力,减少了对石墨片的破碎。尤其是在黄原胶增稠后,磨盘间剪切力通过高粘度溶液更有效传递给石墨片层,提高剥离效率,降低破坏作用。因此,通过磨盘法制备的石墨烯片层较大、平整、不易团聚。而且,黄原胶边缘接枝石墨烯能够更稳定地分散在水中。因此,本发明的黄原胶边缘改性石墨烯在高分子复合材料、吸附材料、污水处理以及增稠助剂等领域有广阔应用。The present invention adopts a grinding disc process, and xanthan gum, graphite and water are cyclically stripped between grinding discs. The shearing action between the fixed grinding disc and the movable grinding disc is transmitted to the graphite sheet through the high-viscosity xanthan gum solution, thereby realizing the stripping preparation of graphene. Compared with methods such as ball milling, sand milling and ultrasound, the grinding disc process effectively utilizes the stripping force between the grinding discs, and reduces the crushing of the graphite sheet. Especially after the xanthan gum is thickened, the shearing force between the grinding discs is more effectively transmitted to the graphite sheet through the high-viscosity solution, thereby improving the stripping efficiency and reducing the destructive effect. Therefore, the graphene sheet prepared by the grinding disc method is larger, smooth and not easy to agglomerate. Moreover, the xanthan gum edge-grafted graphene can be more stably dispersed in water. Therefore, the xanthan gum edge-modified graphene of the present invention has broad applications in the fields of polymer composite materials, adsorbent materials, sewage treatment and thickening aids.
下面结合实施例对本发明作进一步说明,但本发明的范围并不局限于这些实施例。The present invention will be further described below in conjunction with embodiments, but the scope of the present invention is not limited to these embodiments.
以下实施例中的实验试剂除标注自制之外均为市售采购。The experimental reagents in the following examples are all commercially available except those marked as homemade.
实施例中使用的磨盘为自制。The grinding disc used in the examples was homemade.
实施例中使用的红外光谱型号为美国赛默飞Nicolet IS5。The infrared spectrometer used in the examples is the American Thermo Fisher Nicolet IS5.
实施例中使用的扫描电镜型号为日本日立S4800。The scanning electron microscope used in the examples is a Hitachi S4800 from Japan.
实施例1Example 1
将6.0克黄原胶(梅花生物科技集团股份有限公司,MHF-80R)溶解在1000毫升去离子水中,再加入150克100目鳞片石墨(青岛三同石墨有限公司),搅拌均匀。磨盘转速设定为100rpm,循环研磨72小时后,将磨盘加工过的石墨烯悬浮液倒入烧杯中,静置10个小时后,过滤去除沉淀,得到黄原胶边缘接枝石墨烯的稳定水分散液,其中接枝石墨烯的质量分数为2.8%。石墨烯产率约为所加入鳞片石墨质量的20%。图2中1号样品是静置10个月后的黄原胶接枝石墨烯稳定水分散液,未见沉淀。这主要是因为在石墨烯边缘接枝的黄原胶起到稳定分散作用。6.0 grams of xanthan gum (Meihua Biotechnology Group Co., Ltd., MHF-80R) were dissolved in 1000 ml of deionized water, and then 150 grams of 100 mesh flake graphite (Qingdao Santong Graphite Co., Ltd.) were added and stirred. The grinding disc speed was set at 100 rpm. After 72 hours of circulation grinding, the graphene suspension processed by the grinding disc was poured into a beaker. After standing for 10 hours, the precipitation was removed by filtering to obtain a stable aqueous dispersion of xanthan gum edge-grafted graphene, wherein the mass fraction of grafted graphene was 2.8%. The graphene yield was about 20% of the mass of the added flake graphite. Sample No. 1 in Figure 2 is a stable aqueous dispersion of xanthan gum grafted graphene after standing for 10 months, and no precipitation was seen. This is mainly because the xanthan gum grafted on the graphene edge plays a stabilizing dispersion role.
将10mL黄原胶接枝石墨烯水分散液加入200mL去离子水中稀释,然后采用0.22微米孔径的微孔过滤膜减压过滤,最后再用2L去离子水滤除游离的黄原胶,烘干后得到纯化的黄原胶接枝石墨烯。10 mL of xanthan gum grafted graphene aqueous dispersion was added to 200 mL of deionized water for dilution, and then filtered under reduced pressure using a microporous filter membrane with a pore size of 0.22 μm. Finally, 2 L of deionized water was used to filter out free xanthan gum, and purified xanthan gum grafted graphene was obtained after drying.
图3为制备的黄原胶接枝石墨烯的扫描电镜照片,接枝石墨烯的片层平均尺寸约2.9微米。FIG3 is a scanning electron microscope photograph of the prepared xanthan gum grafted graphene, and the average size of the grafted graphene flakes is about 2.9 microns.
图4为制备的黄原胶边缘接枝石墨烯的透射电子显微镜照片。从图片可以看出,石墨烯仅有一层,表明制备的是石墨烯。Figure 4 is a transmission electron microscope photo of the prepared xanthan gum edge-grafted graphene. As can be seen from the picture, there is only one layer of graphene, indicating that graphene is prepared.
图5为制备的黄原胶边缘接枝石墨烯的红外谱图,由于黄原胶接枝率低,官能团的红外吸收峰较弱。图6是对图5的红外谱图的基线做拉直处理后的谱图,放大官能团的吸收峰,以提高分辨力。从图中可以看出各种官能团的吸收峰,醇羟基的伸缩振动在3458cm-1处,亚甲基的伸缩振动在2922cm-1处,苯环骨架振动吸收峰在1622cm-1处,丙酮酸基团和乙酰基基团中甲基的弯曲振动吸收峰在1406cm-1处,D-葡萄糖单元、D-甘露糖单元之间的醚键和醚化反应产生的醚键的伸缩振动在1080cm-1处。红外谱图表明黄原胶接枝到石墨烯。Fig. 5 is the infrared spectrum of the prepared xanthan gum edge grafted graphene. Due to the low grafting rate of xanthan gum, the infrared absorption peak of the functional group is weak. Fig. 6 is the spectrum after the baseline of the infrared spectrum of Fig. 5 is straightened, and the absorption peak of the functional group is amplified to improve the resolution. From the figure, it can be seen that the absorption peaks of various functional groups, the stretching vibration of alcoholic hydroxyl group is at 3458cm - 1, the stretching vibration of methylene is at 2922cm -1 , the vibration absorption peak of benzene ring skeleton is at 1622cm -1 , the bending vibration absorption peak of methyl in pyruvic acid group and acetyl group is at 1406cm -1 , and the stretching vibration of the ether bond between D-glucose unit and D-mannose unit and the ether bond produced by etherification reaction is at 1080cm -1 . The infrared spectrum shows that xanthan gum is grafted to graphene.
图7为纯鳞片石墨和黄原胶边缘接枝石墨烯的热重分析曲线。鳞片石墨几乎没有失重;黄原胶边缘接枝石墨烯在280℃开始分解失重,至330℃几乎不再失重,此时失重3.2%,表明石墨烯接枝黄原胶的质量含量为3.2%。Figure 7 shows the thermogravimetric analysis curves of pure flake graphite and xanthan gum edge-grafted graphene. Flake graphite has almost no weight loss; xanthan gum edge-grafted graphene begins to decompose and lose weight at 280°C, and almost stops losing weight at 330°C, with a weight loss of 3.2%, indicating that the mass content of graphene grafted xanthan gum is 3.2%.
实施例2Example 2
将10.0克黄原胶(梅花生物科技集团股份有限公司,MHF-80R)溶解在1000毫升去离子水中,再加入150克100目鳞片石墨(青岛三同石墨有限公司),搅拌均匀。磨盘转速设定为100rpm,循环研磨100小时后,将磨盘加工过的石墨烯悬浮液倒入烧杯中,静置10个小时后,过滤去除沉淀,得到黄原胶边缘接枝石墨烯的稳定水分散液,其中接枝石墨烯的质量分数为3.0%。根据实施例1的方法纯化,得到黄原胶接枝石墨烯,制备的接枝石墨烯的片层平均尺寸约2.1微米,接枝改性石墨烯中接枝的黄原胶质量含量为4.7%。接枝改性石墨烯产率约为所加入鳞片石墨质量的25%。图2中2号样品为静置10个月后的稳定分散液。10.0 grams of xanthan gum (Meihua Biotechnology Group Co., Ltd., MHF-80R) were dissolved in 1000 ml of deionized water, and then 150 grams of 100 mesh flake graphite (Qingdao Santong Graphite Co., Ltd.) were added and stirred. The grinding disc speed was set at 100 rpm. After 100 hours of circulation grinding, the graphene suspension processed by the grinding disc was poured into a beaker. After standing for 10 hours, the precipitation was filtered and removed to obtain a stable aqueous dispersion of xanthan gum edge-grafted graphene, wherein the mass fraction of the grafted graphene was 3.0%. Purification according to the method of Example 1 obtained xanthan gum grafted graphene, the average size of the lamellae of the prepared grafted graphene was about 2.1 microns, and the xanthan gum mass content grafted in the grafted modified graphene was 4.7%. The grafted modified graphene yield was about 25% of the mass of the added flake graphite. Sample No. 2 in Figure 2 is a stable dispersion after standing for 10 months.
实施例3Example 3
将10.0克黄原胶(梅花生物科技集团股份有限公司,MHF-80R)溶解在1000毫升去离子水中,再加入150克100目鳞片石墨(青岛三同石墨有限公司),搅拌均匀。磨盘转速设定为60rpm,循环研磨100小时后,将磨盘加工过的石墨烯悬浮液倒入烧杯中,静置10个小时后,过滤去除沉淀,得到黄原胶边缘接枝石墨烯的稳定水分散液,其中接枝石墨烯的质量分数为2.5%。根据实施例1的方法纯化,得到黄原胶接枝石墨烯,根据实施例1的方法纯化,得到黄原胶接枝石墨烯,制备出的接枝石墨烯的片层平均尺寸约2.1微米,接枝改性石墨烯中接枝的黄原胶质量含量为3.4%。接枝改性石墨烯产率约为所加入鳞片石墨质量的18%。图2中3号为接枝改性石墨烯样品静置10个月后的稳定分散液,未见沉淀。10.0 grams of xanthan gum (Meihua Biotechnology Group Co., Ltd., MHF-80R) were dissolved in 1000 ml of deionized water, and then 150 grams of 100 mesh flake graphite (Qingdao Santong Graphite Co., Ltd.) were added and stirred. The grinding disc speed was set at 60rpm. After 100 hours of circulation grinding, the graphene suspension processed by the grinding disc was poured into a beaker. After standing for 10 hours, the precipitation was removed by filtration to obtain a stable aqueous dispersion of xanthan gum edge-grafted graphene, wherein the mass fraction of the grafted graphene was 2.5%. Purification according to the method of Example 1 was performed to obtain xanthan gum grafted graphene. Purification according to the method of Example 1 was performed to obtain xanthan gum grafted graphene. The average size of the lamellae of the grafted graphene prepared was about 2.1 microns, and the xanthan gum mass content grafted in the grafted modified graphene was 3.4%. The grafted modified graphene yield was about 18% of the mass of the added flake graphite. No. 3 in Figure 2 is a stable dispersion of the grafted modified graphene sample after standing for 10 months, with no precipitation observed.
实施例4Example 4
将8.0克黄原胶(梅花生物科技集团股份有限公司,MHF-80R)溶解在1000毫升去离子水中,再加入150克100目鳞片石墨(青岛三同石墨有限公司),搅拌均匀。磨盘转速设定为100rpm,循环研磨48小时后,将磨盘加工过的石墨烯悬浮液倒入烧杯中,静置10个小时后,过滤去除沉淀,得到黄原胶边缘接枝石墨烯的稳定水分散液,接枝石墨烯质量分数为2.3%。根据实施例1的方法纯化,得到黄原胶接枝石墨烯,制备的接枝改性石墨烯的片层平均尺寸约2.3微米,接枝改性石墨烯中接枝的的黄原胶质量含量为2.8%。石墨烯产率约为所加入鳞片石墨质量的15%。图2中4号为接枝改性石墨烯样品静置10个月后的稳定水分散液,未见沉淀。8.0 grams of xanthan gum (Meihua Biotechnology Group Co., Ltd., MHF-80R) were dissolved in 1000 ml of deionized water, and then 150 grams of 100 mesh flake graphite (Qingdao Santong Graphite Co., Ltd.) were added and stirred. The grinding disc speed was set to 100rpm. After 48 hours of circulation grinding, the graphene suspension processed by the grinding disc was poured into a beaker. After standing for 10 hours, the precipitation was filtered and removed to obtain a stable aqueous dispersion of xanthan gum edge-grafted graphene, and the grafted graphene mass fraction was 2.3%. Purification according to the method of Example 1 obtained xanthan gum grafted graphene, the average size of the lamellae of the prepared grafted modified graphene was about 2.3 microns, and the xanthan gum mass content grafted in the grafted modified graphene was 2.8%. The graphene yield was about 15% of the mass of the added flake graphite. No. 4 in Figure 2 is a stable aqueous dispersion of the grafted modified graphene sample after standing for 10 months, and no precipitation was seen.
实施例5Example 5
将12.0克黄原胶(梅花生物科技集团股份有限公司,MHF-80R)溶解在1000毫升去离子水中,再加入100克100目膨胀石墨(青岛三同石墨有限公司),搅拌均匀。磨盘转速设定为70rpm,循环研磨72小时后,将磨盘加工过的石墨烯悬浮液倒入烧杯中,静置10个小时后,过滤去除沉淀,得到黄原胶边缘接枝石墨烯的稳定水分散液,接枝石墨烯质量分数为3.5%。根据实施例1的方法纯化,得到黄原胶边缘接枝石墨烯,制备的接枝石墨烯的片层平均尺寸大于3.1微米,接枝石墨烯中黄原胶质量含量为2.6%。石墨烯产率约为所加入鳞片石墨质量的18%。图2中5号为接枝石墨烯样品静置10个月后的稳定分散液,未见沉淀。12.0 grams of xanthan gum (Meihua Biotechnology Group Co., Ltd., MHF-80R) were dissolved in 1000 ml of deionized water, and 100 grams of 100 mesh expanded graphite (Qingdao Santong Graphite Co., Ltd.) were added and stirred. The grinding disc speed was set at 70 rpm. After 72 hours of circulation grinding, the graphene suspension processed by the grinding disc was poured into a beaker. After standing for 10 hours, the precipitation was filtered and removed to obtain a stable aqueous dispersion of xanthan gum edge-grafted graphene, with a grafted graphene mass fraction of 3.5%. Purification according to the method of Example 1 obtained xanthan gum edge-grafted graphene, the average size of the lamellae of the prepared grafted graphene was greater than 3.1 microns, and the xanthan gum mass content in the grafted graphene was 2.6%. The graphene yield was about 18% of the mass of the added flake graphite. No. 5 in Figure 2 is a stable dispersion of the grafted graphene sample after standing for 10 months, with no precipitation.
比较例Comparative Example
在1000毫升去离子水中,加入150克100目鳞片石墨(青岛三同石墨有限公司),搅拌均匀。磨盘转速设定为100rpm,循环研磨100小时后,将磨盘加工过的石墨烯悬浮液倒入烧杯中,静置10个小时后,过滤去除沉淀。只能得到非常少量的石墨烯,小于加入鳞片石墨质量的0.5%。该石墨烯悬浮液仅可稳定保存数天,数天后即可观察到明显的沉淀,一周后几乎全部沉淀。In 1000 ml of deionized water, add 150 g of 100 mesh flake graphite (Qingdao Santong Graphite Co., Ltd.) and stir evenly. The grinding wheel speed is set to 100 rpm. After 100 hours of cyclic grinding, the graphene suspension processed by the grinding wheel is poured into a beaker, left to stand for 10 hours, and filtered to remove the precipitate. Only a very small amount of graphene can be obtained, which is less than 0.5% of the mass of the added flake graphite. The graphene suspension can only be stably stored for a few days, and obvious precipitation can be observed after a few days, and almost all precipitation after a week.
以上已经描述了本发明的各实施例,上述说明是示例性的,并非穷尽性的,并且也不限于所披露的各实施例。在不偏离所说明的各实施例的范围和精神的情况下,对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。The endpoints and any values of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and the individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this article.
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