阅读说明：本技术 一种氮掺杂石墨烯/溶聚丁苯复合材料及其制备方法 (Nitrogen-doped graphene/solution-polymerized butylbenzene composite material and preparation method thereof ) 是由 刘力 李亚思 温世鹏 于 2018-07-09 设计创作，主要内容包括：本发明提供一种氮掺杂石墨烯/溶聚丁苯复合材料,重点解决石墨烯在橡胶中分散性不好的难题。通过对氧化石墨烯进行功能化得到氮掺杂石墨烯,减小氧化石墨烯的层数与缺陷,增加与橡胶的结合力,提高其应用性能,使其易于形成交联的网络结构。氮掺杂石墨烯与白炭黑并用作为补强填料时,可互相插层减少团聚,且带有的氮元素可以与橡胶发生较强的氢键作用,增强填料与橡胶的作用力。本发明氮掺杂石墨烯/溶聚丁苯复合材料由于具有优越的力学性能及自身结构致使其在高性能橡胶补强中有广泛的应用。(The invention provides a nitrogen-doped graphene/solution-polymerized butylbenzene composite material, which mainly solves the problem of poor dispersibility of graphene in rubber. The nitrogen-doped graphene is obtained by functionalizing the graphene oxide, so that the number of layers and defects of the graphene oxide are reduced, the bonding force with rubber is increased, the application performance of the rubber is improved, and a cross-linked network structure is easily formed. When the nitrogen-doped graphene and the white carbon black are used as reinforcing fillers, the nitrogen-doped graphene and the white carbon black can be intercalated with each other to reduce agglomeration, and the nitrogen element can generate a strong hydrogen bond effect with rubber to enhance the acting force of the fillers and the rubber. The nitrogen-doped graphene/solution polymerized butylbenzene composite material has excellent mechanical property and self structure, so that the nitrogen-doped graphene/solution polymerized butylbenzene composite material has wide application in high-performance rubber reinforcement.)

1. The nitrogen-doped graphene/solution-polymerized butylbenzene composite material is characterized by being prepared from the following raw materials in parts by weight:

2. the nitrogen-doped graphene/solution-polymerized butylbenzene composite material according to claim 1, wherein the composite material is prepared from raw materials comprising the following components in parts by weight:

3. the nitrogen-doped graphene/solution-polymerized styrene-butadiene composite material according to claim 1, wherein:

the nitrogen-doped graphene is prepared by the following steps: drying graphene oxide, respectively adding a grinding aid into the graphene oxide and a nitrogen-containing organic compound, then fully mixing the graphene oxide and the nitrogen-containing organic compound, heating under the protection of an inert atmosphere or other atmospheres, then reacting, and finally grinding the obtained solid into powder to obtain the nitrogen-doped graphene, wherein the mass ratio of the graphene oxide to the nitrogen-containing organic compound is 1: 5-1: 50, the heating rate is 1-10 ℃/min, the reaction temperature is 100-600 ℃, and the reaction time is 0.5-5 h.

4. The nitrogen-doped graphene/solution-polymerized styrene-butadiene composite material according to claim 3, wherein:

the thickness of the graphene oxide is 1-100 nm;

the nitrogen-containing organic compound is one or more of melamine, urea, amino acid, nitrate, nitrite, pyridine, acetonitrile, triethylamine and benzidine;

the inert atmosphere is helium, neon, argon, krypton or xenon, and the other atmosphere is nitrogen;

the grinding aid is water, methanol, ethanol, trifluoroethanol, formic acid, triethanolamine, acetic acid, acetone, ethyl acetate, tetrahydrofuran, N-methyl pyrrolidone, diethyl ether, propylene oxide, dichloromethane and trichloromethane.

5. The nitrogen-doped graphene/solution-polymerized styrene-butadiene composite material according to claim 1, wherein:

the vulcanizing agent is sulfur or peroxide crosslinking agent; the accelerator is thiazole, sulfenamide, thiuram, dithiocarbamate, guanidine or xanthate accelerator.

6. The nitrogen-doped graphene/solution-polymerized styrene-butadiene composite material according to claim 1, characterized in that the composite material comprises at least one of the following components, based on 100 parts by weight of solution-polymerized styrene-butadiene rubber:

7. the nitrogen-doped graphene/solution-polymerized styrene-butadiene composite material according to claim 6, wherein:

the anti-aging agent is quinoline, p-phenylenediamine or naphthylamine; the surface modifier is a silane coupling agent.

8. A method for preparing the nitrogen-doped graphene/solution-polymerized butylbenzene composite material according to any one of claims 1 to 7, which comprises the following steps:

plasticating the solution polymerized styrene butadiene rubber according to the amount, adding the components including the nitrogen-doped graphene and the white carbon black, carrying out heat treatment, cooling, adding the accelerator and the vulcanizing agent, mixing uniformly, and vulcanizing.

Technical Field

The invention relates to the field of nano composite materials, in particular to a nitrogen-doped graphene/solution-polymerized butylbenzene composite material and a preparation method thereof.

Background

Graphene Single-layer graphene was first prepared by the university of Manchester, UK by micromechanical exfoliation, graphene being the SP of adjacent carbon atoms²The hybrid orbit is connected by sigma covalent bond, and the six-membered honeycomb monolayer carbon atom structure is the thinnest carbon material in the world and is also a basic unit for constructing other carbon materials. Graphene has unique advantages in electrochemical, thermal, optical and mechanical properties, but its application is limited due to its chemical stability and its surface inactive groups. Graphene oxide is an important derivative of graphene and is composed of single-layer graphite oxide, and the graphene oxide contains a large number of active functional groups such as hydroxyl, carboxyl and epoxy groups, so that the graphene oxide has good modification capability. The graphene oxide can be chemically modified to enhance the binding capacity with a rubber matrix and improve the dispersion in rubber.

Graphite phase carbon nitride (g-C)₃N₄) Is a novel covalent compound with higher hardness, and has attracted wide attention due to the advantages of high chemical stability, wear resistance, simple preparation method, narrower forbidden band width and the like.

The graphite phase carbon nitride has similar graphene six-membered ring network structure and SP²The hybrid structure is easy to carry out composite reaction with graphene due to the graphene-like structure.

Disclosure of Invention

The invention aims to provide nitrogen-doped graphene (g-C)₃N₄the/rGO) composite particles are dispersed in rubber, and the problem of agglomeration of graphene oxide in rubber is mainly solved. The invention is mainly characterized in that g-C₃N₄Compensate the vacancy and the defect of GO, simultaneously carry out partial reduction to graphene oxide, improve the physicochemical property of graphene oxide, add the above-mentioned nitrogen-doped graphene compound into the rubber matrix, because nitrogen element can react with the disulfide bond, form stronger hydrogen bond with rubber, strengthen the crosslinked network, on the other hand, when being used as filler together with white carbon black, the mutual intercalation improves the dispersion, keeps away from the white carbon blackThe aggregation of the separately added rubber matrix inside is avoided.

One purpose of the invention is to provide a nitrogen-doped graphene/solution polymerized butylbenzene composite material, which is prepared from the following raw materials in parts by weight:

wherein, the vulcanizing agent is commonly used in the field, and is preferably sulfur or peroxide crosslinking agent.

The accelerator is selected from the accelerators commonly used in the field, preferably thiazole, sulfenamide, thiuram, dithiocarbamate, guanidine or xanthate accelerators.

The nitrogen-doped graphene can be prepared by adopting a process method which is common in the field, and is preferably prepared by adopting the following steps: drying graphene oxide, respectively adding a grinding aid into the graphene oxide and a nitrogen-containing organic compound, then fully mixing the graphene oxide and the nitrogen-containing organic compound, heating under the protection of an inert atmosphere or other atmospheres, then reacting, and finally grinding the obtained solid into powder to obtain the nitrogen-doped graphene, wherein the mass ratio of the graphene oxide to the nitrogen-containing organic compound is 1: 5-1: 50, the heating rate is 1-10 ℃/min, the reaction temperature is 100-600 ℃, and the reaction time is 0.5-5 h.

Wherein the thickness of the graphene oxide is 1-100 nm.

The nitrogen-containing organic compound is one or more of melamine, urea, amino acid, nitrate, nitrite, pyridine, acetonitrile, triethylamine and benzidine.

The inert atmosphere is helium, neon, argon, krypton or xenon, and the other atmosphere is nitrogen.

The grinding aid is water, methanol, ethanol, trifluoroethanol, formic acid, triethanolamine, acetic acid, acetone, ethyl acetate, tetrahydrofuran, N-methyl pyrrolidone, diethyl ether, propylene oxide, dichloromethane and trichloromethane.

Specifically, the nitrogen-doped graphene (g-C)₃N₄/rGO) can be prepared by the following steps:

and placing the graphene oxide in an oven for drying at the temperature of 25-100 ℃ for 1-10 h. Respectively placing a nitrogen-containing organic compound and graphene oxide in a mortar, adding a small amount of grinding aid for mixing, then placing the nitrogen-containing organic compound and the graphene oxide in a ball mill for rapid ball milling to fully mix the nitrogen-containing organic compound and the graphene oxide, wherein the ball milling speed is 100-500 r/min, and the ball milling time is 1-10 h. Transferring the product into a crucible with a cover, heating the crucible in an inert atmosphere or other atmosphere protection program control box type furnace at a heating rate of 1-10 ℃/min, at a reaction termination temperature of 100-600 ℃ for 0.5-5 h, and finally grinding the obtained solid into powder to obtain g-

C₃N₄/rGO。

The nitrogen-doped graphene/solution-polymerized styrene-butadiene composite material also comprises at least one of the following components in parts by weight based on 100 parts by weight of solution-polymerized styrene-butadiene rubber:

zinc oxide and stearic acid are active agents.

The paraffin is plasticizer, and has effects of resisting ozone oxidation and lubricating.

The anti-aging agent is commonly used in the field, and is preferably quinoline, paraphenylenediamine or naphthylamine.

The surface modifier is selected from surface modifiers commonly used in the field, and is preferably a silane coupling agent.

The invention also aims to provide a preparation method of the nitrogen-doped graphene/solution polymerized butylbenzene composite material, which comprises the following steps:

plasticating the solution polymerized styrene-butadiene rubber according to the amount, adding the components including the nitrogen-doped graphene and the white carbon black, then carrying out heat treatment, cooling, adding the accelerator and the vulcanizing agent, mixing uniformly and vulcanizing.

Preferably, the preparation process is as follows:

firstly, adding a certain amount of solution polymerized styrene-butadiene rubber matrix into a rubber open mill or an internal mixer, then adding zinc oxide, stearic acid, an anti-aging agent, paraffin, white carbon black, nitrogen-doped graphene and a surfactant, placing the mixture into a hot roller open mill, carrying out heat treatment at 100-180 ℃ for 3-10 min, cooling, adding an accelerator and a vulcanizing agent into the open mill or the internal mixer to obtain a nitrogen-doped graphene/solution polymerized styrene-butadiene rubber mixed rubber, and vulcanizing to obtain the nitrogen-doped graphene/solution polymerized styrene-butadiene rubber composite material.

The graphene oxide and g-C of the present invention₃N₄The preparation method has simple system and process and is easy to expand, g-C₃N₄The preparation of the material can obtain g-C with special appearance, size and excellent physical properties by using urea or melamine as a precursor and controlling the properties of raw materials and a reduction method₃N₄a/rGO composite particle.

According to the invention, the graphene oxide is functionalized, so that the number of layers and defects of the graphene oxide are reduced, the bonding force with rubber is increased, the application performance of the rubber is improved, and a cross-linked network structure is easily formed. When the carbon white is used as a reinforcing filler, the carbon white and the carbon black can be intercalated to reduce agglomeration, and the nitrogen element of the nitrogen-doped graphite can generate strong hydrogen bond action with rubber to enhance the acting force of the filler and the rubber.

Therefore, the nitrogen-doped graphite can be used as an excellent reinforcing material to be applied to rubber reinforcement, and the solution polymerized styrene-butadiene rubber composite material with uniform filler dispersion and excellent performance is prepared. The nitrogen-doped graphene/solution polymerized butylbenzene composite material has excellent mechanical property and self structure, so that the nitrogen-doped graphene/solution polymerized butylbenzene composite material has wide application in high-performance rubber reinforcement.

Detailed Description

The present invention will be further described with reference to the following specific embodiments. However, the present invention is not limited to the following examples.

Solution polymerized styrene-butadiene rubber (SSBR, brand 5025, oil-extended 37.5phr, product of Germany Langsheng company); the other raw materials are all obtained in the market.