WO2010045889A1

WO2010045889A1 - Polymer reinforced composite

Info

Publication number: WO2010045889A1
Application number: PCT/CN2009/074622
Authority: WO
Inventors: 陈永胜; 梁嘉杰; 黄毅; 马延风; 张龙; 王燕
Original assignee: Nankai University; Tianjin Pulan Nano Technology Co Ltd
Current assignee: Nankai University; Tianjin Pulan Nano Technology Co Ltd
Priority date: 2008-10-24
Filing date: 2009-10-26
Publication date: 2010-04-29
Anticipated expiration: 2011-04-24
Also published as: CN101381524A

Abstract

A composite comprising functional graphene and water soluble polymer, and preparation method thereof are provided, wherein the content of functional graphene is 0.05-20wt% based on the total weight of the composite. The composite provided exhibits excellent mechanical property.

Description

说明书 Instruction manual

Title of Invention:高分子增强复合材料 Title of Invention: Polymer Reinforced Composites

[i] [i]

[2] [2]

[3] 本发明涉及一种复合材料及其制备方法，特别是一种功能化石墨烯材料与高分子材料的复合材料及其制备方法。 [3] The present invention relates to a composite material and a preparation method thereof, and in particular to a composite material of a functionalized graphene material and a high molecular material and a preparation method thereof.

[4] ¾匕 [4] 3⁄4匕

[5] 水溶性高分子材料是一种在水中能溶解或溶胀而形成溶液或分散液的高分子材料。它具有性能优异、使用方便、有利环境保护等优点，广泛应用于国民经济的各个领域。以聚乙烯醇为例，由于其具有独特的强粘接性、膜柔韧性、平滑性、耐磨性以及经特殊处理具有的耐水性等特点，因此广泛用于生产涂料、粘合剂、纸品加工剂、乳化剂、分散剂、薄膜等产品。因此，对水溶性高分子材料进行改性已成为该领域的重要研究课题。 [5] A water-soluble polymer material is a polymer material that dissolves or swells in water to form a solution or dispersion. It has the advantages of excellent performance, convenient use, and environmental protection, and is widely used in various fields of the national economy. In the case of polyvinyl alcohol, it is widely used in the production of paints, adhesives, and papers because of its unique strong adhesion, film flexibility, smoothness, abrasion resistance, and water resistance due to special treatment. Process agents, emulsifiers, dispersants, films and other products. Therefore, modification of water-soluble polymer materials has become an important research topic in this field.

[6] 最近，由于其优异的性能，单层石墨材料的出现已经引起了很多人的关注。理论和实验数据表明一片完整的单分子厚的单层石墨的机械性能甚至超过了单根的完整的碳纳米管。功能化石墨烯材料是石墨片上接上了一些亲水性官能团（如羟基、羧基、氨基、羰基和环氧基等）或其他官能团的的单层石墨材料。由于这些官能团的存在使得功能化石墨烯材料具有很好的溶解性。 [6] Recently, the appearance of single-layer graphite materials has attracted a lot of attention due to its excellent performance. Theoretical and experimental data indicate that the mechanical properties of a single monolayer of single-layer graphite are even higher than that of a single intact carbon nanotube. Functionalized graphene materials are single-layer graphite materials on which graphite sheets are attached with hydrophilic functional groups (such as hydroxyl, carboxyl, amino, carbonyl, and epoxy groups) or other functional groups. Due to the presence of these functional groups, the functionalized graphene material has good solubility.

[7] 缘于此，本发明人提出本发明。 [7] Accordingly, the inventors have proposed the present invention.

[8] 鍾既 i术 [8] Zhong Yi i

[9] 一方面，本发明提供一种功能化石墨烯与水溶性高分子材料的复合材料，其中所述的功能化石墨烯在整个复合材料中占 0.05-20wt%，水溶性高分子材料占 99.95-80wt 。 [9] In one aspect, the present invention provides a composite material of functionalized graphene and a water-soluble polymer material, wherein the functionalized graphene accounts for 0.05-20% by weight of the entire composite material, and the water-soluble polymer material accounts for 99.95-80wt.

[10] 在本发明的复合材料的一些实施方案中，所述功能化石墨烯的量占整个复合材料量为 0.1-20wt%。在另外一些实施方案中，所述功能化石墨烯的量占整个复合材料量为 0.2-10wt%。在另外一些实施方案中，所述功能化石墨烯的量占整个复合材料量为 0.3-5wt%。 [11] 另一方面，本发明提供一种制备复合材料的方法，包括将适量的功能化石墨烯分散于可溶性高分子材料中。 [10] In some embodiments of the composite of the present invention, the amount of functionalized graphene is from 0.1 to 20% by weight based on the total amount of the composite. In other embodiments, the amount of functionalized graphene is from 0.2 to 10% by weight based on the total amount of the composite. In other embodiments, the amount of functionalized graphene is from 0.3 to 5% by weight based on the total amount of composite. [11] In another aspect, the present invention provides a method of preparing a composite material comprising dispersing an appropriate amount of functionalized graphene in a soluble polymer material.

[12] 在本发明方法的一些实施方案中，包括： [12] In some embodiments of the methods of the invention, the method comprises:

[13] 1 ) 将一定量的功能化石墨烯溶于或分散于水或有机溶剂中； [13] 1) dissolving or dispersing a certain amount of functionalized graphene in water or an organic solvent;

[14] 2 ) 将可溶性高分子材料溶于另外的水或有机溶剂中； [14] 2) dissolving the soluble polymer material in another water or organic solvent;

[15] 3 ) 将两种溶液混合；以及 [15] 3) mixing the two solutions;

[16] 4 ) 的刀 Ogwai shixie将所得的混合液进行处理得到所需的复合材料。 [16] 4) Knife Ogwai shixie treats the resulting mixture to give the desired composite.

在某些实施方式中，对任意的上述步骤 1 ) -3 ) ，可以通过加热等方式提高功能化石墨烯或可溶性高分子材料在溶剂中的溶解或分散性。在另外一些实施方案中，对任意的上述步骤 1 ) -3 ) ，可通过超声处理。 In some embodiments, for any of the above steps 1) to 3), the solubility or dispersibility of the functionalized graphene or the soluble polymer material in a solvent can be improved by heating or the like. In other embodiments, any of the above steps 1) -3) may be treated by sonication.

[18] 在一方面，本发明提供一种提高水溶性高分子材料的机械性能的方法，包括将适量的功能化石墨烯分散于可溶性高分子材料中。 [18] In one aspect, the present invention provides a method of improving the mechanical properties of a water soluble polymeric material comprising dispersing an appropriate amount of functionalized graphene in a soluble polymeric material.

[19] 在本发明中，所述的水溶性高分子材料通常是指在水中能溶解或溶胀而形成溶液或分散液的高分子，包括（但不限制）：聚乙烯醇，聚乙烯亚胺，聚丙烯酸，聚苯乙烯磺酸钠，聚丙烯酰胺，聚氧化乙烯，分子量为 2-12万。 [19] In the present invention, the water-soluble polymer material generally refers to a polymer capable of dissolving or swelling in water to form a solution or dispersion, including (but not limited to): polyvinyl alcohol, polyethyleneimine , polyacrylic acid, sodium polystyrene sulfonate, polyacrylamide, polyethylene oxide, molecular weight of 2-12 million.

[20] 应该理解，尽管没有具体描述，除非互相抵触，组成本发明上述几个方面的技术特征可以相互组合。如本发明的提高水溶性高分子材料的机械性能的方法中，在本发明其它方面限定的水溶性高分子材料和功能化石墨烯材料等成分或工艺条件同样可以用于该方案。 [20] It should be understood that, although not specifically described, unless otherwise contradictory, the technical features of the above aspects of the invention may be combined with each other. In the method of improving the mechanical properties of the water-soluble polymer material of the present invention, components or process conditions such as a water-soluble polymer material and a functionalized graphene material defined in other aspects of the present invention can be used in the same manner.

[21] 本发明提供的含功能化石墨烯与水溶性高分子的复合材料的机械性能有 [21] The mechanical properties of the composite material containing functionalized graphene and water-soluble polymer provided by the present invention are

10-100%的提高。以功能化石墨烯 /聚乙烯醇复合材料为例，当功能化石墨烯材料的含量为 0.7wt (重量）％吋，其杨氏模量提高超过 60%，拉伸强度增超过 70%。并且，功能化石墨烯 /聚乙烯醇的复合材料的杨氏模量的实验值与用 Halpin-Tsai公式模拟的计算值非常匹配，说明了功能化石墨烯与聚乙烯醇基体之间有很强的相互作用。 10-100% improvement. Taking the functionalized graphene/polyvinyl alcohol composite as an example, when the content of the functionalized graphene material is 0.7 wt%, the Young's modulus is increased by more than 60%, and the tensile strength is increased by more than 70%. Moreover, the experimental value of the Young's modulus of the functionalized graphene/polyvinyl alcohol composite material is very well matched with the calculated value simulated by the Halpin-Tsai formula, indicating that there is a strong relationship between the functionalized graphene and the polyvinyl alcohol matrix. Interaction.

[22] 國綱 [22] National Gang

[23] 图 1为不同功能化石墨烯材料含量的聚乙烯醇复合材料的应力 -应变曲线图。 [23] Figure 1 is a graph of stress-strain curves for polyvinyl alcohol composites with different functionalized graphene materials.

[24] 图 2为不同功能化石墨烯材料含量的聚乙烯醇复合材料的杨氏模量曲线。 [25] 具体实施方式 [24] Figure 2 shows the Young's modulus curves of polyvinyl alcohol composites with different functionalized graphene materials. [25] Specific implementation

[26] 下面通过实施例对本发明进行具体描述，本实施例只用于对本发明进行进一步的说明，不能理解为对本发明保护范围的限制。本领域的技术人员根据本申请公开的内容做出一些非本质性改进和调整，均应属于本发明的范围。 The invention is described in detail below with reference to the accompanying drawings. Those skilled in the art will make some non-essential improvements and adjustments in light of the disclosure of the present application, which are all within the scope of the present invention.

[27] 定义 [27] Definition

[28] 本申请中，如无特别说明，术语'功能化石墨烯 '或'功能化石墨烯材料'是指其分子骨架由六角形晶格排列的石墨烯原子组成的二维平面材料，其单个石墨片面积在 10nm²到 400μηι²之间，单片厚度在 0.34到 4nm之间，并且其中引入羧基、羟基、氨基、环氧键、磺酸基、苯基异氰酸酯、噻吩、吡咯、苯胺和 Z或含 6 到 18个碳的长链垸基等官能团至少一种后的改性石墨烯或石墨烯材料，其在水或与水互溶的有机溶剂中的溶解度在 O.lmg/ml以上。所述有机溶剂包括但不限于甲醇，乙醇，丙醇，丙酮， N，N-二甲基甲酰胺，二甲基亚砜。 [28] In the present application, the term 'functionalized graphene' or 'functionalized graphene material' refers to a two-dimensional planar material whose molecular skeleton is composed of hexagonal lattice-arranged graphene atoms, unless otherwise specified. The single graphite sheet has an area of 10 nm ² to 400 μm ² , a single piece thickness of 0.34 to 4 nm, and a carboxyl group, a hydroxyl group, an amino group, an epoxy bond, a sulfonic acid group, a phenyl isocyanate, a thiophene, a pyrrole, an aniline, and the like. Z or a functional group having a long chain thiol group of 6 to 18 carbons, at least one post-modified graphene or graphene material having a solubility in water or a water-miscible organic solvent of 0.1 mg/ml or more. The organic solvent includes, but is not limited to, methanol, ethanol, propanol, acetone, N,N-dimethylformamide, dimethyl sulfoxide.

[29] 制备实施例 1： [29] Preparation Example 1:

[30] 功能化石墨烯材料的制备 [30] Preparation of functionalized graphene materials

[31] 将 5 g石墨和 3.8 g NaN0₃加入三口烧瓶中，然后加入 370 mL浓硫酸。之后于冰水浴中，边搅拌边缓缓加入 23 g KMn0₄，室温电动搅拌 7天。将反应溶液缓慢加入到 500 mL 5wt 的稀硫酸中，温度控制在 98 ° C。反应液在该温度下再继续搅拌 2 h，然后降温至 60 ° C。加入 15mL H₂0₂ (30%水溶液），在 60 ° C 保持 2 h。冷至室温，然后利用离心方法除去其中的杂质。在 8，000 rpm下离心 20 min，除去上清液。加入 3 wt H₂SOV0.5 wt H₂0₂的混合液，强烈搅拌 30 min , 重复 10次。之后使用 3 wt%的盐酸重复上述步骤 2次，使用蒸馏水重复 2次。然后将溶剂除去获得功能化石墨烯材料。 [31] 5 g of graphite and 3.8 g of NaN0 _{3 were} placed in a _three- necked flask, followed by the addition of 370 mL of concentrated sulfuric acid. Then, in an ice water bath, 23 g of KMn0 _{4 was} slowly added while stirring, and the mixture was stirred at room temperature for 7 days. The reaction solution was slowly added to 500 mL of 5 wt of dilute sulfuric acid at a temperature of 98 ° C. The reaction solution was further stirred at this temperature for 2 h and then cooled to 60 ° C. 15 mL H ₂ O ₂ (30% in water) was added and kept at 60 ° C for 2 h. It was cooled to room temperature and then the impurities were removed by centrifugation. The supernatant was removed by centrifugation at 8,000 rpm for 20 min. A mixture of 3 wt H ₂ SOV 0.5 wt H ₂ 0 ₂ was added and stirred vigorously for 30 min, repeated 10 times. Thereafter, the above procedure was repeated twice using 3 wt% hydrochloric acid, and repeated twice using distilled water. The solvent is then removed to obtain a functionalized graphene material.

[32] 实施例 1 : [32] Example 1 :

[33] 含 0.3wt%功能化石墨烯的聚乙烯醇复合材料 [33] Polyvinyl alcohol composite containing 0.3wt% functionalized graphene

[34] 将 3mg制备实施例 1制得的功能化石墨烯材料溶解于 6ml蒸馏水中并超声半小吋。在这过程中功能化石墨烯材料均匀稳定地分散在水溶液中。 [34] 3 mg of the functionalized graphene material prepared in Preparation Example 1 was dissolved in 6 ml of distilled water and ultrasonicated for half an hour. The functionalized graphene material is uniformly and stably dispersed in the aqueous solution during this process.

在 9 0 ° C下将 lg聚乙烯醇（分子量： 3-5万，醇解度： 86-89% , 购于阿尔法公司，以下实施例相同）溶解到 14ml蒸馏水中，待完全溶解后将聚乙烯醇溶液冷却到 40。 C。 The lg polyvinyl alcohol (molecular weight: 3-5 million, alcoholysis degree: 86-89%, purchased from Alpha Company, the same in the following examples) was dissolved in 14 ml of distilled water at 90 ° C, and was dissolved after being completely dissolved. Vinyl alcohol The liquid is cooled to 40. C.

[36] 然后将分散好的功能化石墨烯水溶液滴加到聚乙烯醇溶液中。将混合溶液继续超声半小吋后，浇铸在聚四氟基板上成膜，并在 60 ° C下真空烘烤至质量基本上没有变化即可。 [36] The dispersed aqueous solution of the functionalized graphene is then added dropwise to the polyvinyl alcohol solution. After the mixed solution was further ultrasonicated for a half time, it was cast on a polytetrafluoro substrate to form a film, and vacuum-baked at 60 ° C until the quality was basically unchanged.

[37] 经拉伸试验测试 0.3wt%的功能化石墨烯 I聚乙烯醇薄膜比纯聚乙烯醇薄膜的拉伸强度提高了 36%，杨氏模量提高了 18%。 [37] Tensile test test 0.3wt% of functionalized graphene I polyvinyl alcohol film has a 36% increase in tensile strength and a Young's modulus of 18% over pure polyvinyl alcohol film.

[38] 实施例 2： [38] Example 2:

[39] 含 0.5wt%功能化石墨烯的聚乙烯醇复合材料 [39] Polyvinyl alcohol composite containing 0.5wt% functionalized graphene

[40] 将 5mg制备实施例 1制得的功能化石墨烯材料溶解于 6ml蒸馏水中并超声半小吋，在这过程中功能化石墨烯材料均匀稳定地分散在水溶液中。 [5] 5 mg of the functionalized graphene material prepared in Preparation Example 1 was dissolved in 6 ml of distilled water and ultrasonicated for a half time, during which the functionalized graphene material was uniformly and stably dispersed in the aqueous solution.

[41] 在 9 0 ° C下将 lg聚乙烯醇溶解到 14ml蒸馏水中，待完全溶解后将聚乙烯醇溶液冷却到 40 ° C。 [41] Dissolve lg polyvinyl alcohol in 14 ml of distilled water at 90 ° C. After complete dissolution, cool the polyvinyl alcohol solution to 40 ° C.

[42] 然后将分散好的功能化石墨烯水溶液滴加到聚乙烯醇溶液中。将混合溶液继续超声半小吋后，浇铸在聚四氟基板上成膜，并在 60 ° C下真空烘烤至质量基本上没有变化即可。 [42] The dispersed aqueous solution of the functionalized graphene is then added dropwise to the polyvinyl alcohol solution. After the mixed solution was further ultrasonicated for a half time, it was cast on a polytetrafluoro substrate to form a film, and vacuum-baked at 60 ° C until the quality was basically unchanged.

[43] 经拉伸试验测试含 0.5wt%功能化石墨烯的聚乙烯醇薄膜比纯聚乙烯醇薄膜的拉伸强度提高了 47%，杨氏模量提高了 35%。 [43] The tensile strength test showed that the tensile strength of the polyvinyl alcohol film containing 0.5 wt% of functionalized graphene was 47% higher than that of the pure polyvinyl alcohol film, and the Young's modulus was increased by 35%.

[44] 实施例 3 ： [44] Example 3:

[45] 含 0.7wt%功能化石墨烯的聚乙烯醇复合材料 [45] Polyvinyl alcohol composite containing 0.7wt% functionalized graphene

[46] 将制备实施例 1得到的 7mg功能化石墨烯材料溶解于 6ml蒸馏水中并超声半小吋，在这过程中功能化石墨烯材料均匀稳定地分散在水溶液中。 The 7 mg of the functionalized graphene material obtained in Preparation Example 1 was dissolved in 6 ml of distilled water and ultrasonicated for a half time, in which the functionalized graphene material was uniformly and stably dispersed in the aqueous solution.

[47] 在 90 ° C下将 lg聚乙烯醇溶解到 14ml蒸馏水中，待完全溶解后将聚乙烯醇溶液冷却到 40。 C。 [47] Dissolve lg polyvinyl alcohol in 14 ml of distilled water at 90 ° C. After completely dissolving, cool the polyvinyl alcohol solution to 40. C.

[48] 然后将分散好的功能化石墨烯水溶液滴加到聚乙烯醇溶液中。将混合溶液继续超声半小吋后，浇铸在聚四氟基板上成膜，并在 60 ° C下真空烘烤至质量基本上没有变化即可。 [48] The dispersed aqueous solution of the functionalized graphene is then added dropwise to the polyvinyl alcohol solution. After the mixed solution was further ultrasonicated for a half time, it was cast on a polytetrafluoro substrate to form a film, and vacuum-baked at 60 ° C until the quality was basically unchanged.

[49] 经拉伸试验测试含 0.7wt%功能化石墨烯的聚乙烯醇薄膜比纯聚乙烯醇薄膜的拉伸强度提高了 76%，杨氏模量提高了 62%。从图 1和图 2 (横坐标已转化为体积参量）可以看出，随着功能化石墨烯含量的增加，聚乙烯醇复合材料的机械强度不断的增加并且在含量为 0.7wt%吋达到最大值，说明功能化石墨烯对聚乙烯醇基体的机械性能起到了很好的增强作用 [49] The tensile strength test showed that the tensile strength of the polyvinyl alcohol film containing 0.7 wt% of functionalized graphene was 76% higher than that of the pure polyvinyl alcohol film, and the Young's modulus was increased by 62%. It can be seen from Fig. 1 and Fig. 2 (the abscissa has been converted into the volume parameter) that as the functionalized graphene content increases, the mechanical strength of the polyvinyl alcohol composite material continuously increases and reaches a maximum at a content of 0.7 wt%. Value, indicating that functionalized graphene has a good effect on the mechanical properties of the polyvinyl alcohol matrix.

Claims

Claim

[Claim 1] A composite material comprising functionalized graphene and a water-soluble polymer material, wherein the soluble functionalized graphene accounts for the total weight of the composite material

0.05-20wt.

[Claim 2] The composite material according to claim 1, wherein the functionalized graphene accounts for 0.1 to 20% by weight based on the total weight of the composite material.

[Claim 3] The composite material according to claim 1, wherein the functionalized graphene accounts for 0.2 to 10% by weight based on the total weight of the composite material.

[Claim 4] The composite according to claim 1, wherein said functionalized graphene comprises from 0.3 to 5% by weight based on the total weight of the composite.

[Claim 5] The composite material according to any one of claims 1 to 4, wherein the water-soluble polymer material is selected from the group consisting of polyvinyl alcohol, polyethyleneimine, polyacrylic acid, sodium polystyrene sulfonate, polyacrylamide or Polyethylene oxide with a molecular weight between 20,000 and 120,000.

[Claim 6] The composite material according to claim 5, wherein the water-soluble polymer material is polyvinyl alcohol, has a molecular weight of 2 to 120,000, and has a degree of alcoholysis of 70 to 90%, preferably, molecular weight. : 3-5 million, alcoholysis: 86-89%.

[Claim 7] A method of preparing a water-soluble polymer composite comprising dispersing an appropriate amount of functionalized graphene in a water-soluble polymer material.

[Claim S] The method according to claim 7, comprising:

1) dissolving or dispersing a certain amount of functionalized graphene in water or an organic solvent;

2) dissolving the soluble polymer material in another water;

3) mixing the two solutions;

4) Knife Ogwai shixie treats the resulting mixture to give the desired composite.

[Claim 9] The method according to claim 8, wherein any of the steps 1) - 3) is performed by heating or ultrasonication.

[Claim 10] The method according to claim 9 or 10, wherein the step 4) is to prepare a composite film material by spraying, spin coating and casting after volatilizing the solvent in the mixing.

[Claim 11] The method according to claim 8, wherein step 1) adding the functionalized graphene material to 1

In water, sonicated for 20-100 min.

[Claim 12] The method according to claim 8, wherein the step 3) comprises agitation for 20-30 min and ultrasonic treatment for 0.5-2 h.

[Claim 13] The method according to any of claims 9-12, wherein the water-soluble polymer material is selected from the group consisting of polyvinyl alcohol, polyethyleneimine, polyacrylic acid, sodium polystyrene sulfonate, polyacrylamide or Polyethylene oxide with a molecular weight between 20,000 and 120,000.

[Claim 14] The method according to claims 9-13, wherein the organic solvent is selected from the group consisting of methanol, ethanol, propanol, acetone, N,N-dimethylformamide or dimethyl sulfoxide.

[Claim 15] The method according to claims 7-13, wherein the water-soluble polymer material is selected from the group consisting of polyvinyl alcohol, polyethyleneimine, polyacrylic acid, sodium polystyrene sulfonate, polyacrylamide or polyethylene oxide. The molecular weight is between 20,000 and 120,000.

[Claim 16] The method according to claim 15, wherein the water-soluble polymer material is polyvinyl alcohol having a molecular weight of from 2 to 120,000, a degree of alcoholysis of from 70 to 90%, preferably, a molecular weight : 3-5 million, alcoholysis: 86-89%.

[Claim 17] A method of improving the mechanical properties of a water-soluble polymer material, comprising dispersing an appropriate amount of functionalized graphene in a soluble polymer material.

[Claim 18] The method according to claim 17, comprising:

1) dissolving or dispersing the functionalized graphene in water or an organic solvent;

2) dissolving the soluble polymer material in another water;

3) mixing the two solutions; and 4) the knife Ogwai shixie to treat the resulting mixture to obtain the desired polymer material.