Preparation method and application of graphene anion composite material additive

Abstract

The invention discloses a preparation method and application of a graphene negative ion composite material additive, wherein the borosilicate is ground into a nano-scale material and then water is added to prepare a borosilicate pretreatment liquid, and the borosilicate pretreatment liquid is evenly mixed with a graphene dispersion liquid to obtain a graphene negative ion composite material additive; the graphene negative ion composite material additive can be used to prepare graphene negative ion curtain cloth, graphene negative ion wall cloth, and graphene negative ion interior wall latex paint. The graphene negative ion composite material additive prepared by the invention can effectively release negative oxygen ions, adsorb harmful substances in the air, and is conducive to improving and treating indoor and outdoor air environments.

Description

Technical Field

[0001] The invention relates to the technical field of graphene composite materials, and in particular to a preparation method and application of a graphene anion composite material additive. Background Art

[0002] Formaldehyde (HCHO) is one of the main pollutants emitted into indoor air by building decoration materials. It can cause allergic symptoms at very low concentrations and is also a carcinogen. Nitric oxide (NO), nitrogen dioxide (NO2) and sulfur dioxide (SO2) are also major outdoor air pollutants. Therefore, the decomposition of harmful substances such as HCHO, NO, NO2, SO2 and O3 indoors and outdoors is of great significance to people's health. At present, titanium dioxide (TiO2) is usually used as a decomposition material for HCHO, NO2, NO, SO2 and O3. Although nano-scale TiO2 can better demonstrate its catalytic ability, its small size will cause it to agglomerate and reduce its catalytic performance. It also requires the action of ultraviolet light for catalytic cracking and cannot release negative ions for a long time. Nanosilver is another substance used for catalytic degradation of HCHO, NO2, NO, SO2, O3, etc., but it will also agglomerate during the application process and requires the action of ultraviolet light for catalytic cracking. At present, in the process of environmental application, it tends to be carried out under visible light conditions, so nanosilver is difficult to meet practical applications.

[0003] Graphene has a large specific surface area and can effectively inhibit the agglomeration of loaded materials. Single-layer graphene has good electrical conductivity and good thermal sensitivity, which can cause polar ions to vibrate at equilibrium positions and cause changes in dipole moments. It can also generate resonance radiation between its own free ions, impure ions and ionic substances, which can affect the polar vibration of ionic bonds in the cross-linking of organic and inorganic molecules, forming a strong radiation broadband and effectively releasing negative oxygen ions. At the same time, graphene itself has good adsorption capacity and can better adsorb harmful substances in the air.

[0004] The present invention mixes a single-layer graphene and a ring-structured silicate material to prepare a graphene negative ion composite material additive, which is loaded onto related products to ensure that the product can quickly and long-lastingly release negative oxygen ions under visible light conditions and degrade harmful gases such as HCHO, NO2, NO, SO2, O3, etc. Summary of the invention

[0005] The purpose of the present invention is to overcome the deficiencies of the above-mentioned prior art and provide a preparation method and application of a graphene negative ion composite material additive. The prepared graphene negative ion composite material additive can effectively release negative oxygen ions and adsorb harmful substances in the air, which is beneficial to improve and manage the indoor and outdoor air environment.

[0006] In order to achieve the above object, the present invention adopts the following technical solution:

[0007] A method for preparing a graphene anion composite material additive comprises the following steps:

[0008] S1. Adding or not adding triethanolamine to borosilicate, grinding into nano-scale material, and then adding pure water to mix, to prepare a borosilicate pretreatment liquid containing or not containing triethanolamine;

[0009] S2, adding the monolayer graphene oxide powder to deionized water or polyvinyl alcohol aqueous solution, stirring and dispersing, and preparing a graphene dispersion containing or not containing polyvinyl alcohol;

[0010] S3, mixing the borosilicate pretreatment liquid not containing triethanolamine with the graphene dispersion liquid not containing polyvinyl alcohol, adding an emulsifier, and continuing to mix evenly to obtain a graphene negative ion composite material additive; or mixing the borosilicate pretreatment liquid containing triethanolamine with the graphene dispersion liquid containing polyvinyl alcohol, heating and reacting, to obtain a graphene negative ion composite material additive.

[0011] The borosilicate is a mixture of aluminum borosilicate, sodium borosilicate and magnesium borosilicate, and the borosilicate pretreatment solution contains 0.05 wt % of borosilicate.

[0012] The particle size of the borosilicate powder after grinding is 100~500 nm.

[0013] The concentration of single-layer graphene oxide in the graphene dispersion is 2~6 mg / ml.

[0014] The borosilicate pretreatment liquid and the graphene dispersion liquid are mixed in a mass ratio of 1:3.

[0015] When the borosilicate pretreatment liquid without triethanolamine is mixed with the graphene dispersion liquid without polyvinyl alcohol, the mass concentration of the added emulsifier is 25-30%, and the amount of the emulsifier added is 0.1-0.5% of the mass of the graphene dispersion liquid.

[0016] The emulsifier is one of sodium lauryl sulfate and octylphenol polyoxyethylene ether.

[0017] When triethanolamine is added for grinding of borosilicate, the triethanolamine is 0.05-0.1% of the mass of the borosilicate.

[0018] When the borosilicate pretreatment solution containing triethanolamine is mixed with the graphene dispersion containing polyvinyl alcohol for reaction, the reaction temperature is 50-60° C.; the concentration of polyvinyl alcohol in the graphene dispersion containing polyvinyl alcohol is 8-10 mg / ml.

[0019] The invention discloses an application of a graphene negative ion composite material auxiliary agent. The graphene negative ion composite material auxiliary agent can be used to prepare graphene negative ion curtain cloth, graphene negative ion wall cloth and graphene negative ion interior wall latex paint. The graphene negative ion curtain cloth is obtained by uniformly spraying the graphene negative ion composite material auxiliary agent on the curtain cloth, and then subjecting the curtain cloth to high-temperature shaping, high-temperature steam stretching and drying. The graphene negative ion composite material auxiliary agent is mixed with a water-based polyurethane waterproofing agent to prepare a waterproof coating, and then the waterproof coating is dip-coated on the wall cloth, and then subjecting the wall cloth to high-temperature shaping to obtain the graphene negative ion wall cloth. The graphene negative ion interior wall latex paint is obtained by uniformly mixing the graphene negative ion composite material auxiliary agent with interior wall latex paint.

[0020] The beneficial effects of the present invention are as follows: the graphene negative ion composite material is prepared with a single layer of graphene oxide and a silicate material with a ring structure mainly characterized by boron as main components, and can effectively release negative oxygen ions, degrade harmful gases such as HCHO, NO2, NO, SO2, O3, etc., and better adsorb harmful substances in the air. Furthermore, triethanolamine is used as a grinding aid to grind borosilicate, which improves the uniformity of the particle size distribution of borosilicate, makes the borosilicate more evenly dispersed, and greatly reduces the agglomeration of particles; polyvinyl alcohol aqueous solution is used as a dispersant to promote the dispersion of monolayer graphene oxide powder and reduce particle agglomeration; and the borosilicate pretreatment liquid containing triethanolamine and the graphene dispersion liquid containing polyvinyl alcohol are mixed to prepare the graphene negative ion composite material, so that the borosilicate and graphene in the graphene negative ion composite material system are more evenly dispersed. At the same time, triethanolamine can functionally modify part of the graphene, enhance the adsorption of graphene, and promote the release of negative oxygen ions from the graphene negative ion composite material. In addition, the presence of a small amount of polyvinyl alcohol in the graphene negative ion composite material forms a composite material, which can increase the water resistance of graphene negative ion curtain cloth, graphene negative ion wall cloth, and graphene negative ion interior wall latex paint. Triethanolamine-modified graphene and polyvinyl alcohol can play a synergistic role and further improve the release effect of negative oxygen ions. DETAILED DESCRIPTION

[0021] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments:

[0022] The preparation of the graphene anion composite material additive of the present invention comprises the following steps:

[0023] S1. Add or not add triethanolamine to borosilicate, grind into nano-scale material, then add pure water for mixing, and prepare borosilicate pretreatment liquid without or with triethanolamine. Wherein, borosilicate is a mixture of aluminum borosilicate, sodium borosilicate and magnesium borosilicate, and the particle size of the powder after grinding of borosilicate is 100-500 nm; the borosilicate pretreatment liquid contains 0.05wt% borosilicate. When triethanolamine is added for grinding of borosilicate, the triethanolamine is 0.05-0.1% of the mass of borosilicate.

[0024] S2. Add the monolayer graphene oxide powder to deionized water or polyvinyl alcohol aqueous solution, stir and disperse, and prepare a graphene dispersion without or with polyvinyl alcohol. The concentration of monolayer graphene oxide in the graphene dispersion is 2-6 mg / ml. When the monolayer graphene oxide powder is added to the polyvinyl alcohol aqueous solution, the concentration of polyvinyl alcohol in the graphene dispersion is 8-10 mg / ml. The polyvinyl alcohol aqueous solution is prepared by mixing polyvinyl alcohol and water, stirring, heating to 90°C and keeping warm for 0.8h.

[0025] S3. Mix the borosilicate pretreatment liquid containing no triethanolamine and the graphene dispersion liquid containing no polyvinyl alcohol in a mass ratio of 1:3, add an emulsifier (the emulsifier is one of sodium lauryl sulfate and octylphenol polyoxyethylene ether, the mass concentration of the added emulsifier is 25-30%, and the amount of the emulsifier added is 0.1-0.5% of the mass of the graphene dispersion liquid), continue to mix evenly, and obtain a graphene negative ion composite material additive; or mix the borosilicate pretreatment liquid containing triethanolamine and the graphene dispersion liquid containing polyvinyl alcohol in a mass ratio of 1:3, heat the reaction at 50-60°C, and obtain a graphene negative ion composite material additive.

[0026] The graphene negative ion composite material additive prepared by the above method can be used for the production and preparation of graphene negative ion curtain fabrics, graphene negative ion wall fabrics, and graphene negative ion interior wall latex paints.

[0027] The specific embodiments are as follows:

[0028] Example 1

[0029] A. Preparation of graphene anion composite material additives:

[0030] 1) Grind borosilicate containing aluminum borosilicate, sodium borosilicate and magnesium borosilicate for 8 h to prepare nano-scale materials with a particle size of 100-500 nm, and mix and stir the nano-scale materials with pure water at high speed for 100 min to prepare borosilicate pretreatment solution; the borosilicate pretreatment solution contains 0.02% aluminum borosilicate, 0.01% sodium borosilicate and 0.02% magnesium borosilicate by mass.

[0031] 2) The monolayer graphene oxide powder (thickness distribution between 0.8 and 2 nm, particle size distribution between 1 and 5 μm) was uniformly dispersed in deionized water to obtain a graphene dispersion with a graphene concentration of 3 mg / ml.

[0032] 3) Add 25 parts by mass of the silicate pretreatment liquid to 75 parts by mass of the graphene dispersion, mix at high speed for 100 min, then add an emulsifier (the emulsifier is sodium dodecyl sulfate, the mass concentration is 25%, and the addition amount is 0.2% of the mass of the graphene dispersion), and ultrasonically mix at room temperature to obtain a graphene negative ion composite material additive.

[0033] B. Application of graphene anion composite material additives:

[0034] 200g of the prepared graphene anion composite material additive was evenly sprayed on a 10 m 2 Curtain fabric (the amount of graphene negative ion composite material additive on the curtain fabric is 20g / m 2 ), the curtain fabric is high-temperature fixed at 100℃-140℃, and the fabric is kept flat by high-temperature steam stretching. After drying, it can be made into graphene negative ion curtain fabric with the function of releasing negative ions.

[0035] According to the inspection of China National Testing Center (report number: WT2023B03F00312), the material induced negative air ions of 5.20×10 7 ions / (s·m 2 ).

[0036] Example 2

[0037] A. Preparation of graphene anion composite material additives:

[0038] 1) grinding borosilicate containing aluminum borosilicate, sodium borosilicate and magnesium borosilicate for 7 hours to prepare nano-scale materials with a particle size of 100-500 nm, and mixing and stirring the nano-scale materials with pure water at high speed for 120 minutes to prepare a borosilicate pretreatment solution;

[0039] The borosilicate pretreatment solution contains 0.02% aluminum borosilicate, 0.01% sodium borosilicate and 0.02% magnesium borosilicate by mass fraction.

[0040] 2) The monolayer graphene oxide powder (thickness distribution between 0.8 and 2 nm, particle size distribution between 1 and 5 μm) is uniformly dispersed in deionized water to obtain a graphene dispersion with a graphene concentration of 5 mg / ml.

[0041] 3) Add 25 parts by mass of the silicate pretreatment liquid to 75 parts by mass of the graphene dispersion, mix at high speed for 120 min, then add an emulsifier (the emulsifier is sodium dodecyl sulfate, with a mass concentration of 30%, and the addition amount is 0.3% of the mass of the graphene dispersion), and mix by ultrasonication to obtain a graphene negative ion composite material additive.

[0042] B. Application of graphene anion composite material additives:

[0043] 1 part by mass of graphene negative ion composite material additive is mixed with 5 parts by mass of water-based polyurethane waterproofing agent (purchased from Zhejiang Jili New Materials Co., Ltd., model number is resin 1005) to pre-form a wall cloth waterproof coating, which is then injected into a dipping and rolling tank. The wall cloth is passed through a rolling mill at a uniform speed and then shaped at a high temperature of 200°C-230°C to produce a graphene negative ion wall cloth with the function of releasing negative oxygen ions.

[0044] According to the inspection of China National Inspection and Testing Center, the material generates 5.13×10 7 ions / (s·m 2 ).

[0045] Example 3

[0046] A. Preparation of graphene anion composite material additives:

[0047] 1) Grind borosilicate containing aluminum borosilicate, sodium borosilicate and magnesium borosilicate for 8 h to prepare nano-scale materials with a particle size of 100-500 nm, and mix and stir the nano-scale materials with pure water at high speed for 90 min to prepare a borosilicate pretreatment solution; the borosilicate pretreatment solution contains 0.02% aluminum borosilicate, 0.01% sodium borosilicate and 0.02% magnesium borosilicate.

[0048] 2) The monolayer graphene oxide powder (thickness distribution between 0.8 and 2 nm, particle size distribution between 1 and 5 μm) was uniformly dispersed in deionized water to obtain a graphene dispersion with a graphene concentration of 4 mg / ml.

[0049] 3) 25 parts by mass of silicate pretreatment liquid were added to 75 parts by mass of graphene dispersion liquid, and then mixed at high speed for 110 min. Then, an emulsifier (the emulsifier was octylphenol polyoxyethylene ether with a mass concentration of 28% and an addition amount of 0.5% of the mass of the graphene dispersion liquid) was added and ultrasonically mixed to obtain a graphene negative ion composite material additive.

[0050] B. Application of graphene anion composite material additives:

[0051] Mix 2 parts by mass of graphene negative ion composite material additive with 8 parts by mass of interior wall latex paint (purchased from Nippon Paint Co., Ltd., model Nippon Paint New Shishili), and stir well to obtain a mixed paint with the function of releasing negative oxygen ions for painting.

[0052] According to the inspection of China National Testing Center (report number: WT2022B03F00332), the amount of negative ions in the air is 376 / (s·cm 2 ).

[0053] Example 4

[0054] A. Preparation of graphene anion composite material additives:

[0055] 1) Borosilicate containing aluminum borosilicate, sodium borosilicate and magnesium borosilicate was mixed with triethanolamine and ground for 5 h (triethanolamine was 0.1% of the mass of borosilicate) to prepare a nanoscale material with a particle size of 100-500 nm, which was mixed and stirred with pure water at high speed for 60 min to prepare a borosilicate pretreatment solution; the borosilicate pretreatment solution contained 0.02% aluminum borosilicate, 0.01% sodium borosilicate and 0.02% magnesium borosilicate by mass.

[0056] 2) The monolayer graphene oxide powder (thickness distribution between 0.8 and 2 nm, particle size distribution between 1 and 5 μm) was uniformly dispersed in a polyvinyl alcohol aqueous solution to obtain a graphene dispersion with a graphene concentration of 4 mg / ml. The polyvinyl alcohol concentration in the graphene dispersion was 8 mg / ml.

[0057] 3) 25 parts by mass of the silicate pretreatment liquid was added to 75 parts by mass of the graphene dispersion liquid, mixed at high speed for 60 minutes, and then heated at 60° C. for 10 hours to obtain a graphene anion composite material additive.

[0058] B. Application of graphene anion composite material additives:

[0059] 2 parts by mass of graphene negative ion composite material additives are mixed with 8 parts by mass of interior wall latex paint, and after fully stirring, graphene negative ion interior wall latex paint with the function of releasing negative oxygen ions can be obtained for painting.

[0060] After inspection, it was found that the amount of negative oxygen ions induced by the material prepared in this embodiment was 5.47% higher than that in Example 1 within the same period of time; the induced negative oxygen ion release time was extended by 15 days compared with that in Example 3; after water resistance test, there were no bubbles, cracks, whitening and other undesirable phenomena after immersion for 52 hours, while bubbles appeared in the paint film in Example 3 after immersion for 30 hours.

[0061] Comparative Example 1

[0062] A graphene anion composite material additive was prepared according to the method of Example 4 and used to prepare graphene anion curtain fabric, except that a borosilicate pretreatment solution was prepared according to step 1) of Example 3 (i.e., grinding without adding triethanolamine).

[0063] After testing, the amount of negative oxygen ions induced by the material prepared in comparative example 1 was 1.01% higher than that in example 3 within the same period of time; the induced negative oxygen ion release time was extended by 3 days compared with that in example 3; and bubbles, cracks, and whitening appeared after immersion for 40 hours.

[0064] Comparative Example 2

[0065] A graphene anion composite material additive was prepared according to the method of Example 4 and used to prepare graphene anion curtain fabric, except that the graphene dispersion was prepared according to step 2) of Example 3 (ie without adding polyvinyl alcohol).

[0066] After testing, it was found that within the same period of time, the amount of negative oxygen ions induced by the material prepared in Comparative Example 2 was 1.29% higher than that in Example 3; the induced negative oxygen ion release time was extended by 5 days compared with that in Example 3; and bubbles, cracks, and whitening appeared after immersion for 35 hours.

[0067] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a graphene anion composite material additive, characterized in that: The following steps are involved: S1. Add triethanolamine to borosilicate, grind into nano-scale material, then add pure water to mix, and prepare borosilicate pretreatment liquid containing triethanolamine; the triethanolamine is 0.05-0.1% of the mass of borosilicate; S2, adding the monolayer graphene oxide powder to a polyvinyl alcohol aqueous solution, stirring and dispersing, to obtain a graphene dispersion containing polyvinyl alcohol; the concentration of polyvinyl alcohol in the graphene dispersion containing polyvinyl alcohol is 8-10 mg / ml; S3, mixing the borosilicate pretreatment liquid containing triethanolamine with the graphene dispersion liquid containing polyvinyl alcohol, heating them for reaction, and obtaining a graphene anion composite material additive.

2. A method for preparing a graphene anion composite material additive as claimed in claim 1, characterized in that: The borosilicate is a mixture of aluminum borosilicate, sodium borosilicate and magnesium borosilicate, and the borosilicate pretreatment solution contains 0.05 wt % of borosilicate.

3. A method for preparing a graphene anion composite material additive as claimed in claim 1, characterized in that, The particle size of the borosilicate powder after grinding is 100~500 nm.

4. A method for preparing a graphene anion composite material additive as claimed in claim 1, characterized in that, The concentration of single-layer graphene oxide in the graphene dispersion is 2~6 mg / ml.

5. A method for preparing a graphene anion composite material additive as claimed in claim 1, characterized in that, The borosilicate pretreatment liquid and the graphene dispersion liquid are mixed in a mass ratio of 1:

3.

6. A method for preparing a graphene anion composite material additive as claimed in claim 1, characterized in that: When the borosilicate pretreatment liquid containing triethanolamine and the graphene dispersion liquid containing polyvinyl alcohol are mixed and reacted, the reaction temperature is 50-60°C.

7. An application of a graphene anion composite material additive prepared by the method according to any one of claims 1 to 6, characterized in that: The graphene negative ion composite material additive can be used to prepare graphene negative ion curtain fabric, graphene negative ion wall fabric, and graphene negative ion interior wall latex paint; The graphene negative ion curtain cloth is obtained by uniformly spraying the graphene negative ion composite material additive on the curtain cloth, and then subjecting the curtain cloth to high-temperature shaping, high-temperature steam stretching, and drying. The graphene negative ion wall cloth is obtained by mixing the graphene negative ion composite material additive with a water-based polyurethane waterproofing agent to prepare a waterproof coating, and then applying the waterproof coating to the wall cloth and subjecting the wall cloth to high-temperature shaping. The graphene negative ion interior wall latex paint is obtained by uniformly mixing the graphene negative ion composite material additive with interior wall latex paint.