阅读说明：本技术 一种改性石墨烯和含有该改性石墨烯浆料的制备方法 (Modified graphene and preparation method of slurry containing modified graphene ) 是由 马金华 于 2019-11-11 设计创作，主要内容包括：本发明提供了一种改性石墨烯和含有该改性石墨烯浆料的制备方法为：取鳞片状石墨粉、改性剂、蒸馏水和硼酸溶液置于不锈钢高压瓶中,往不锈钢高压瓶中充装液态气体,摇匀静置。将不锈钢高压瓶连接固态气体制备机器,制备固态气体。将固态气体置于紫外光清洗机内进行高能紫外照射,剥离出少层甚至单层改性石墨烯,直到固态气体完全消失后继续紫外辐照一段时间制备得到所述的改性石墨烯,将改性石墨烯继续在紫外灯下曝照,得到改性石墨烯在中间体于真空中保存,该制备改性石墨烯及其分散浆的方法高效环保,同时该改性石墨烯浆料分散性极好,具备表面功能化特性,同时与纳米钛、硅发生键合接枝改性形成钛硅改性石墨烯三元复合新型材料。(The invention provides a modified graphene and a preparation method of slurry containing the modified graphene, which comprises the following steps: putting the scaly graphite powder, the modifier, the distilled water and the boric acid solution into a stainless steel high-pressure bottle, filling liquid gas into the stainless steel high-pressure bottle, shaking up and standing. And connecting the stainless steel high-pressure bottle with a solid gas preparation machine to prepare the solid gas. The preparation method of the modified graphene and the dispersion slurry thereof is efficient and environment-friendly, and meanwhile, the modified graphene slurry has excellent dispersibility and surface functionalization characteristics, and is bonded, grafted and modified with nano titanium and silicon to form the titanium-silicon modified graphene ternary composite novel material.)

1. A preparation method of modified graphene is characterized by comprising the following steps: the preparation method of the modified graphene comprises the following steps:

s1, placing the scaly graphite powder, the silane coupling agent, the distilled water and the boric acid solution with the mass concentration of 1-2 mol/L into a stainless steel high-pressure bottle, sealing, and slowly pumping air out of the stainless steel high-pressure bottle, wherein the vacuum degree in the stainless steel high-pressure bottle is-0.09-0.1 MPA;

s2, filling liquid gas into the stainless steel high-pressure bottle in the step S1, shaking uniformly and standing for 20-28 h;

s3, connecting the stainless steel high-pressure bottle in the step S2 with a solid gas preparation machine to prepare solid gas;

s4, sequentially placing the solid gas obtained in the step S3 in ultraviolet cleaners with wave bands of 185nm and 254nm for ultraviolet high-energy radiation, peeling off graphene sheets through micro-explosion, simultaneously performing functional modification on the graphene sheets and the solid gas to form carbonyl and carbon hydroxyl, and continuously performing grafting reaction on the carbonyl and the carbon hydroxyl generated on the surfaces of the graphene sheets and silicon hydroxyl formed by hydrolysis of silicon hydroxyl compounds or modifiers under the high-energy radiation to obtain a modified graphene crude product;

s5, continuously exposing the modified graphene crude product obtained in the step S4 under an ultraviolet lamp for 20-60 min, removing organic matters mixed on the surface of the modified graphene crude product, continuously completing the grafting reaction of carbonyl formed by functional modification on the surface of the modified graphene crude product obtained in the step S4 and silicon hydroxyl formed by hydrolysis of a modifier under high-energy radiation to obtain the modified graphene, and storing the modified graphene in vacuum to be used as an intermediate for preparing modified graphene slurry.

2. The method for preparing modified graphene according to claim 1, wherein the method comprises the following steps: the modified graphene is prepared from the following materials in parts by weight:

3. the method for preparing modified graphene according to claim 2, wherein the method comprises the following steps: the particle size of the flaky graphite powder is 1000-3000 meshes.

4. The method for preparing modified graphene according to claim 2, wherein the method comprises the following steps: the liquid gas is any one of liquid carbon dioxide, ozone and liquid nitrogen.

5. The method for preparing modified graphene according to claim 2, wherein the method comprises the following steps: the modifier is at least one of a silane coupling agent or a compound containing a silicon hydroxyl group.

6. The method for preparing modified graphene according to claim 2, wherein the method comprises the following steps: the silane coupling agent is at least one of low molecular silica sol, siloxane resin, amino silane, epoxy silane and mercapto silane.

7. The method for preparing modified graphene according to claim 1, wherein the method comprises the following steps: the size of the solid gas in the step S3 is (80-120) mm (40-60) mm (10-30) mm.

8. The method for preparing the modified graphene paste according to any one of claims 1 to 7, wherein the modified graphene paste comprises: the preparation method of the modified graphene slurry containing the modified graphene comprises the following steps:

s1, adding pure nano titanium powder, a silane coupling agent and an organic solvent into a beaker, uniformly mixing, then putting the modified graphene into the beaker, dispersing by adopting ultrasonic waves, finally adding distilled water, and immediately putting the mixture into a stainless steel autoclave for sealing;

s2, placing the stainless steel autoclave in the step S1 in an oven at the temperature of 110-120 ℃ for heat preservation for 6-12 hours for sufficient reaction, and then cooling to 20-30 ℃ and taking out materials to obtain the slurry containing the modified graphene.

9. The method for preparing the slurry containing the modified graphene according to claim 8, wherein: the material of the slurry containing the modified graphene comprises the following components in parts by weight

10. The method for preparing the slurry containing the modified graphene according to claim 9, wherein: the organic solvent is at least one of absolute ethyl alcohol, acetone and methyl pyrrolidone.

Technical Field

The invention relates to the field of preparation of modified graphene, in particular to a preparation method of modified graphene and a preparation method of slurry containing the modified graphene.

Background

The corrosion of materials, particularly steel materials, is extremely remarkable for national economic loss, reaches 3-5% of the total value of national economy, accidents and indirect loss caused by material corrosion are difficult to estimate, the corrosion situation of the materials in the fields of petroleum, refining, chemical industry, metallurgy, electric power, environmental protection, ocean engineering and the like is more severe, the corrosion resistance by adopting a coating technology is the most economic and directly effective mode at present, but the corrosion resistance applied to an anticorrosive coating is mainly based on two points: the coating material based on the shielding function mainly comprises micaceous iron, glass flake, graphene and the like, and the coating material based on the electrochemical protection mechanism mainly comprises zinc, aluminum, iron oxide red, chromate, phosphate, organic corrosion inhibitor and the like. In the field of direct contact with chemical corrosive media such as acid and alkaline substances, an electrochemical protection mechanism coating material is difficult to be sufficient, two types of advanced coating materials are mainly used at present, one type is a graphene technology, and the other type is a titanium nano polymer technology, the two types of advanced coating materials are widely used in the field of severe corrosion at present, and a certain application effect is achieved. Therefore, how to solve the dispersion stability of graphene in the coating is a very critical problem, the existing graphene slurry technology is a technical route of firstly preparing graphene and then modifying, however, powder is agglomerated, if the slurry prepared by redispersion modification is difficult to open a lamellar structure again, modification cannot be uniformly carried out on each graphene structure, so that the modified titanium-silicon graphene slurry which is easy to disperse and difficult to agglomerate is prepared, and the problem of agglomeration and sedimentation of graphene in the coating is urgently solved. Therefore, the two technologies also have technical bottlenecks which are not solved yet, and five main key performance points required by a long-acting heavy-duty anticorrosive coating are difficult to meet simultaneously: the coating is ultra-compact, the coating components are stable, the adhesive force and the wet film adhesive force are ultra-strong, the electrochemical protection function is realized, and the internal stress of the coating material is reduced.

Disclosure of Invention

The invention aims to provide a preparation method of modified graphene and a preparation method of modified graphene slurry containing the modified graphene, and aims to provide a high-efficiency and environment-friendly preparation method of modified graphene, wherein the modified graphene has surface functionalization, can be conveniently dispersed and grafted in various high polymer media, and can be effectively coated with other nano-material composite grafting materials without forming a carbon negative electrode, and the specific contents of the invention are as follows:

the invention provides a preparation method of modified graphene, which is technically characterized by comprising the following steps: the preparation method of the modified graphene comprises the following steps:

s1, placing the scaly graphite powder, the silane coupling agent, the distilled water and the boric acid solution with the mass concentration of 1-2 mol/L into a stainless steel high-pressure bottle, sealing, and slowly pumping air out of the stainless steel high-pressure bottle, wherein the vacuum degree in the stainless steel high-pressure bottle is-0.09-0.1 MPA;

s2, filling liquid gas into the stainless steel high-pressure bottle in the step S1, shaking uniformly and standing for 20-28 h;

s3, connecting the stainless steel high-pressure bottle in the step S2 with a solid gas preparation machine to prepare solid gas;

s4, sequentially placing the solid gas obtained in the step S3 in ultraviolet cleaners with wave bands of 185nm and 254nm for ultraviolet high-energy radiation to generate micro-explosion and strip out modified graphene sheets, meanwhile, finishing functional modification with the solid gas to form carbonyl and carbon hydroxyl, and continuously performing grafting reaction on the carbonyl, the carbon hydroxyl and the like generated on the surfaces of the modified graphene and silicon hydroxyl formed by hydrolysis of silicon hydroxyl compounds or modifiers under the high-energy radiation to obtain a crude modified graphene product;

s5, continuously exposing the modified graphene crude product obtained in the step S4 under an ultraviolet lamp for 20-60 min, removing organic substances included on the surface of the modified graphene, continuously performing functional modification to form carbonyl, carbon hydroxyl and the like, and performing grafting reaction with a silicon hydroxyl compound formed by hydrolysis of a silicon hydroxyl compound or a modifying agent or a silicon hydroxyl formed by hydrolysis of the modifying agent under high-energy radiation to obtain the modified graphene, storing the modified graphene in vacuum to be used as an intermediate for preparing modified graphene slurry, and only completing preparation and initial modification of the modified graphene.

In some embodiments of the present invention, the material for preparing the modified graphene comprises the following components in parts by weight:

in some embodiments of the present invention, the particle size of the flaky graphite powder is 1000 to 3000 mesh.

In some embodiments of the present invention, the liquid gas is any one of liquid carbon dioxide, ozone and liquid nitrogen.

In some embodiments of the present invention, the modifying agent is at least one of a silane coupling agent or a compound containing a silicon hydroxyl group.

In some embodiments of the present invention, the silane coupling agent is at least one of low molecular weight silica sol, siloxane resin, aminosilane, epoxysilane, and mercaptosilane, but the functional modifier used in the preparation of the modified graphene powder must be different from the functional modifier functional group in the formulation of the titanium silicon modified graphene ternary composite slurry in the next step, for example, the amino modifier is used in the preparation of the modified graphene powder, and the epoxy or mercaptosilane coupling agent is used in the preparation of the titanium silicon modified graphene ternary composite slurry, which are sequentially similar to each other. .

In some embodiments of the present invention, the solid gas in step S3 has a size of (80-120) mm (40-60) mm (10-30) mm.

The invention also provides a preparation method of the slurry containing the modified graphene, which has the technical points that: the preparation method of the modified graphene slurry containing the modified graphene comprises the following steps:

s1, adding high-purity nano titanium powder, a silane coupling agent and an organic solvent into a beaker, uniformly mixing, then putting the modified graphene into the beaker, dispersing by adopting ultrasonic waves, finally adding distilled water, and immediately putting the mixture into a stainless steel autoclave for sealing;

s2, placing the stainless steel autoclave in the step S1 in an oven at 110-120 ℃ for heat preservation for 6-12 hours for sufficient reaction, then cooling to 20-30 ℃, taking out materials to obtain the modified graphene-containing slurry, and finally completing modification of the modified graphene in the step to form the modified graphene-containing slurry.

The titanium silicon modified graphene slurry is prepared by organically bonding silicon titanium carbon taking modified graphene as a carrier in a high-energy physical and chemical modification and high-temperature high-pressure hydrothermal mode, a silicon carbon-silicon titanium-carbon titanium ternary composite modified graphene nano high-molecular metal hybrid polymer is prepared, then the polymer is used as a modifier of an anticorrosive coating, and a special high-molecular epoxy resin and a curing agent are compounded to prepare the silicon titanium carbon composite modified graphene nano anticorrosive coating, the titanium silicon modified graphene nano anticorrosive coating is a high-new material technological product combining modified graphene and titanium and silicon nano polymer technologies, the compactness of a coating is greatly improved through the super-strong permeability resistance of the modified graphene and a titanium and silicon high-molecular nano polymer network structure, wherein the titanium and silicon nano are chemically bonded with the high-molecular resin, the coating has super-strong adhesive force and wet film adhesive force, and the corrosion resistance of the modified graphene and titanium are exerted at the same time, the structure and the components of the coating are long-acting and stable and are not corroded, so that the modified graphene modified nano heavy-duty anticorrosive material has excellent corrosion resistance.

In some embodiments of the present invention, the material of the slurry containing modified graphene is composed of the following components in parts by weight

In some embodiments of the present invention, the organic solvent is at least one of absolute ethyl alcohol, acetone, and methyl pyrrolidone, it is to be emphasized that the modifier is at least one of low molecular silica sol, siloxane resin, and functional modifier such as aminosilane, epoxysilane, and mercaptosilane, but the functional modifier used in the preparation of the modified graphene powder must be different from the functional modifier functional group in the formulation of the titanium-silicon-modified graphene ternary composite slurry in the next step, and if an amino modifier is used in the preparation of the modified graphene powder, an epoxy group or mercaptosilane coupling agent is used in the preparation of the titanium-silicon-modified graphene ternary composite slurry, which is similar to that in the above order.

Compared with the prior art, the invention has the beneficial effects that:

1. according to the efficient and environment-friendly preparation method of the modified graphene, the modified graphene has surface functionalization, can be conveniently dispersed and grafted in various high polymer media, and can be effectively coated with other nano-material composite grafts without forming a carbon negative electrode.

2. The efficient and environment-friendly preparation method of the modified graphene is free of emission and pollution, and the yield is close to 100%.

3. According to the invention, the high-quality few-layer modified graphene is prepared by adopting a two-step method, the modified graphene prepared by an ultraviolet energy exposure micro-explosion method has complete and undamaged lamellar layers, and meanwhile, the number of lamellar layers is small, and the modified graphene is simultaneously modified, oxidized and modified in the preparation process, grafted with a silicon molecular modifier, so that agglomeration is avoided, and the modified graphene is easy to disperse.

4. The invention adopts a high-temperature high-pressure hydrothermal method for further modification grafting, and simultaneously the titanium silicon nano material is compounded to form a ternary compound modified graphene coated novel material, so that the grafting is firm, and meanwhile, the slurry formed by the formula and the process can be used in a water-oil paint system and is not required to be subdivided into slurry used for water-based and oil-based metal anticorrosive paint.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention will be more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.