阅读说明：本技术 一种可降解苯系物的室内涂料及其制备方法 (Indoor coating capable of degrading benzene series and preparation method thereof ) 是由 史蕾 王洁 荆通 薛小倩 李淑鑫 刘洪亮 于 2021-06-30 设计创作，主要内容包括：本发明涉及涂料技术领域,尤其涉及一种可降解苯系物的室内涂料及其制备方法,将苯丙乳液和有机硅氧烷改性聚合物乳液混拼,实现两者功能的互补,在达到完好漆膜的同时,还能使涂料具有更好的耐水、耐沾污和耐热性能；同时添加了以氧化石墨烯和二氧化钛的复合物为主要成分的环保粉,使涂料具备了独特的光学、物理、力学和电子性能,对可见光的吸收率更强,电子传导率更高,能有效实现苯系物的催化降解,光催化反应效率更高,对苯系物的降解效果更好；涂料中的各种组分相互配合,相互作用,使制得的产品沸点高,混溶性好,挥发速率适中,还具有优异的聚结和偶合能力,涂膜的流平性、光泽度、丰满度突出,符合室内环境对涂料的需求。(The invention relates to the technical field of coatings, in particular to an indoor coating capable of degrading benzene series and a preparation method thereof, wherein a styrene-acrylic emulsion and an organic siloxane modified polymer emulsion are mixed to realize the complementation of the functions of the styrene-acrylic emulsion and the organic siloxane modified polymer emulsion, so that the coating has better water resistance, stain resistance and heat resistance while a complete paint film is achieved; meanwhile, the environment-friendly powder taking the compound of the graphene oxide and the titanium dioxide as the main component is added, so that the coating has unique optical, physical, mechanical and electronic properties, has stronger absorptivity to visible light and higher electronic conductivity, can effectively realize the catalytic degradation of benzene series, has higher photocatalytic reaction efficiency and better degradation effect on the benzene series; the components in the coating are matched and interacted with each other, so that the prepared product has the advantages of high boiling point, good miscibility, moderate volatilization rate, excellent coalescence and coupling capability, outstanding leveling property, glossiness and fullness of a coating film and accordance with the requirement of indoor environment on the coating.)

1. The indoor coating capable of degrading the benzene series is characterized by comprising the following components in percentage by mass: 16-22% of styrene-acrylic emulsion, 5-10% of organic siloxane modified polymer emulsion, 16-21% of titanium dioxide, 20-35% of heavy calcium carbonate, 2-5% of environment-friendly powder, 1-2% of film-forming auxiliary agent, 0.05-0.1% of pH regulator, 0.6-1% of wetting dispersant, 0.3-0.5% of cellulose, 0.1-0.3% of defoaming agent, 0.6-1% of preservative, 0.2-0.3% of thickening agent and 15-30% of water, wherein the environment-friendly powder is a compound of graphene oxide and titanium dioxide.

2. The indoor paint capable of degrading benzene compounds according to claim 1, wherein graphene oxide in the environment-friendly powder is graphene oxide prepared by Hummers method, and the titanium dioxide is nano titanium dioxide prepared by sol-gel method, wherein the mass ratio of the graphene oxide to the nano titanium dioxide is 1: 4-6.

3. The indoor paint capable of degrading benzene series according to claim 2, wherein the preparation method of the environment-friendly powder comprises the following steps:

step A: mixing graphene oxide with ultrapure water, carrying out ultrasonic crushing for 20-30min, carrying out solid-liquid separation to obtain a graphene oxide solution, and heating the graphene oxide solution to boiling for later use;

and B: mixing titanium dioxide and ultrapure water, carrying out ultrasonic crushing for 20-30min, carrying out solid-liquid separation to obtain a titanium dioxide solution, heating the titanium dioxide solution to 85-95 ℃, and adding the titanium dioxide solution into the boiling graphene oxide solution within 25-35min to obtain a hydrolysate;

and C: heating the hydrolysate to 150-160 ℃ at the speed of 0.8-1.2 ℃/min, and then carrying out hydrothermal reaction for 10-12 h; washing the obtained reaction product, drying for 20-30h in an environment of 75-85 ℃, calcining at 450-460 ℃ after grinding, and preserving heat for 2-2.5h to obtain the environment-friendly powder.

4. The indoor paint capable of degrading benzene series according to claim 1, wherein the titanium dioxide is rutile titanium dioxide; and/or

The pH regulator is 2-amino-2-methyl-1-propanol.

5. The indoor paint capable of degrading benzene series according to claim 1, wherein the film forming aid is alcohol ester twelve.

6. The indoor paint capable of degrading benzene series according to claim 1, wherein the wetting dispersant is a non-ionic wetting agent.

7. The indoor paint capable of degrading benzene series according to claim 1, wherein the cellulose is hydroxyethyl cellulose.

8. The indoor paint capable of degrading benzene series according to claim 1, wherein the defoaming agent is a mineral oil defoaming agent; and/or

The preservative is a mildew-proof and algae-proof preservative.

9. The benzene series-degradable indoor paint of claim 1, wherein the thickener is an alkali swelling thickener.

10. A preparation method of an indoor coating capable of degrading benzene series is characterized by comprising the following steps:

s1: preparing raw materials according to the formula amount of the indoor coating capable of degrading the benzene series according to any one of claims 1 to 9, sequentially adding the cellulose, the pH regulator, the wetting dispersant, the film-forming assistant and the defoaming agent into 2/3-5/6 deionized water which is equal to the total amount of the deionized water, and stirring at a stirring speed of 300-600r/min to obtain a mixture;

s2: increasing the stirring speed to 600-1000r/min, and sequentially adding the titanium dioxide, the environment-friendly powder and the coarse whiting into the mixture obtained in S1 to obtain paint slurry;

s3: pulping the paint paste at the stirring speed of 800-;

s4: and reducing the stirring speed to 800r/min, sequentially adding the rest deionized water, the styrene-acrylic emulsion, the organic siloxane modified polymer emulsion, the preservative and the thickening agent into the slurry after the S3 pulping, and continuously stirring until the stormer viscosity of the obtained coating is 105-110KU at 25 ℃, thereby obtaining the indoor coating of the degradable benzene series.

Technical Field

The invention relates to the technical field of coatings, in particular to an indoor coating capable of degrading benzene series and a preparation method thereof.

Background

With the rapid development of economy in China, the living standard of people is remarkably improved. Researches show that people spend more than 70% of the time indoors on average, the indoor air quality directly influences the body health of people, pollution caused in the indoor decoration process causes more and more people to feel uneasy, and reports of diseases induced by organic pollutants generated in the decoration process are more rare.

Benzene series is one of typical gas pollutants generated in the decoration process, belongs to strong carcinogenic substances, and can destroy the respiratory system and the hematopoietic system of a human body after invading the human body, inhibit the hematopoietic function of the human body, even cause leukemia and the like. Moreover, the benzene series also has the characteristics of wide sources, difficult degradation, high toxicity and great environmental hazard. For the treatment of benzene series, the common methods in the prior art include chemical oxidation, biological oxidation and the like, but the methods have low treatment efficiency and poor effect, are easy to cause secondary pollution, and cannot be widely popularized. The development and application of the environmental self-cleaning material become a research hotspot at home and abroad, and the research on the indoor coating capable of degrading benzene series is imperative.

Disclosure of Invention

Aiming at the technical problems that benzene series generated in indoor decoration in the prior art can not be effectively treated and can have great threat to human health after entering a human body, the invention provides the indoor coating capable of degrading the benzene series and the preparation method thereof, which not only meet the performance requirement of the indoor coating, but also have good photocatalytic degradation performance and can realize high-efficiency catalytic degradation of the benzene series.

In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:

the embodiment of the invention provides an indoor coating capable of degrading benzene series, which comprises the following components, by mass, 16% -22% of styrene-acrylic emulsion, 5% -10% of organic siloxane modified polymer emulsion, 16% -21% of titanium dioxide, 20% -35% of triple superphosphate, 2% -5% of environment-friendly powder, 1% -2% of film-forming auxiliary agent, 0.05% -0.1% of pH regulator, 0.6% -1% of wetting dispersant, 0.3% -0.5% of cellulose, 0.1% -0.3% of defoamer, 0.6% -1% of preservative, 0.2% -0.3% of thickener and 15% -30% of water, wherein the environment-friendly powder is a compound of graphene oxide and titanium dioxide.

Compared with the prior art, the styrene-acrylic emulsion and the organic siloxane modified polymer emulsion are mixed and fused to realize function complementation, and the coating has better water resistance, stain resistance and heat resistance while achieving a perfect paint film; meanwhile, the environment-friendly powder taking the compound of the graphene oxide and the titanium dioxide as the main component is added, so that the coating has unique optical, physical, mechanical and electronic properties, has stronger absorptivity to visible light and higher electronic conductivity, can effectively realize the catalytic degradation of benzene series, has higher photocatalytic reaction efficiency and better degradation effect on the benzene series; the components in the coating are matched and interacted with each other, so that the prepared product has the advantages of high boiling point, good miscibility, moderate volatilization rate, excellent coalescence and coupling capability, outstanding leveling property, glossiness and fullness of a coating film and accordance with the requirement of indoor environment on the coating.

Preferably, the graphene oxide is prepared by a Hummers method, and the titanium dioxide is nano titanium dioxide prepared by a sol-gel method, wherein the mass ratio of the graphene oxide to the nano titanium dioxide is 1: 4-6.

Preferably, the specific preparation method of the environment-friendly powder comprises the following steps:

step A: mixing graphene oxide with ultrapure water, carrying out ultrasonic crushing for 20-30min, carrying out solid-liquid separation to obtain a graphene oxide solution, and heating the graphene oxide solution to boiling for later use; wherein the solid-liquid separation mode can be selected to centrifuge for 10min at the rotating speed of 4000 r/min;

and B: mixing titanium dioxide and ultrapure water, carrying out ultrasonic crushing for 20-30min, carrying out solid-liquid separation to obtain a titanium dioxide solution, heating the titanium dioxide solution to 85-95 ℃, and adding the titanium dioxide solution into the boiling graphene oxide solution within 25-35min to obtain a hydrolysate;

and C: heating the hydrolysate to 150-160 ℃ at the speed of 0.8-1.2 ℃/min, and then carrying out hydrothermal reaction for 10-12 h; washing the obtained reaction product, drying for 20-30h in the environment of 75-85 ℃, calcining in the environment of 450-460 ℃ after grinding, and preserving heat for 2-2.5h to obtain the environment-friendly powder.

The preparation process of the optimized environment-friendly powder enables the nano titanium dioxide and the graphene oxide to be fully compounded, and the prepared environment-friendly powder is large in particle and has an obvious lamellar structure. The coating has a plurality of pore structures in space, plays a certain promoting role in the photocatalysis of titanium dioxide, and further improves the degradation rate of the coating on benzene series in the air.

Preferably, the titanium dioxide is rutile type titanium dioxide.

Preferably, the pH adjusting agent is 2-amino-2-methyl-1-propanol.

Preferably, the coalescent is an alcohol ester twelve.

Preferably, the wetting and dispersing agent is a water-soluble nonionic wetting agent, and specifically, a nonionic wetting agent X405 can be selected.

The water-soluble nonionic wetting agent is more suitable for emulsion paint and water-based paint systems, has ultrahigh HLB (hydrophile-lipophile balance) emulsification value and wetting property, can effectively improve the stability of water-based paint, accelerates the wetting process of the surface of pigment and filler, and improves the dispersion efficiency.

Preferably, the cellulose is hydroxyethyl cellulose, and particularly 250HBR can be selected.

Preferably, the defoaming agent is a mineral oil defoaming agent, and specifically, a molecular-grade defoaming agent A10 of New Hichwa Material company can be selected.

In the preparation process of the emulsion, the mineral oil defoaming agent has higher foam breaking speed and more obvious foam breaking effect on the emulsion.

Preferably, the preservative is a mildew and algae resistant preservative, and particularly EPW from Torrel (Sol) is selected.

The algae-proof and mildew-proof preservative has high active component content, stronger color stability, good ultraviolet resistance, leaching resistance and heat resistance, and is more suitable for indoor environment.

Preferably, the thickener is an alkali swelling thickener, and specifically, an anionic alkali swelling thickener ASE60 of the American Rohm and Haas chemical can be selected.

The alkali swelling thickener has good stability, good thickening performance and excellent rheological property, and has certain effects of adjusting HLB value and improving water separation and delamination of the coating.

The application also provides a preparation method of the indoor coating capable of degrading the benzene series, which specifically comprises the following steps:

s1: preparing raw materials according to the formula amount, sequentially adding the cellulose, the pH regulator, the wetting dispersant, the film-forming assistant and the defoaming agent into 2/3-5/6 deionized water which is equivalent to the total amount of the deionized water, and stirring at the stirring speed of 300-600r/min to obtain a mixture;

s2: increasing the stirring speed to 600-1000r/min, and sequentially adding the titanium dioxide, the environment-friendly powder and the heavy calcium into the mixture to obtain paint slurry;

s3: pulping the paint paste at the stirring speed of 800-;

s4: and reducing the stirring speed to 800r/min, sequentially adding the rest deionized water, the styrene-acrylic emulsion, the organic siloxane modified polymer emulsion, the preservative and the thickening agent into the slurry after the S23 pulping, and continuously stirring until the stormer viscosity of the obtained coating is 105-110KU at 25 ℃, thereby obtaining the indoor coating of the degradable benzene series.

Drawings

In order to make the objects, technical solutions and advantages of the present invention more apparent and to more clearly describe the technical solutions of the present invention, the drawings used in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings may be obtained based on these drawings without creative efforts.

FIG. 1 is an infrared spectrum of nano titanium dioxide in an eco-friendly powder composition used in the examples of the present invention;

FIG. 2 is a standard curve showing the relationship between the benzene concentration and the peak area in the measurement example of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Benzene series is a strong carcinogen, also belong to one of typical gas pollutants produced in the course of finishing, seriously endanger the health of human body, it is difficult to degrade, the toxicity is great, the characteristic with great environmental hazard, the existing benzene series processing method has chemical oxidation and biological oxidation, etc., but the application and popularization of these methods are influenced by the defect such as low treatment efficiency, poor effect, serious secondary pollution, etc., the development and application of the self-cleaning material of environment has become a research hotspot at home and abroad, it is imperative to study an indoor coating that can degrade benzene series.

In order to solve the technical problems of low treatment efficiency, poor effect and serious secondary pollution existing in the treatment method of the benzene series in the prior art, the invention provides an indoor coating capable of degrading the benzene series, the indoor paint capable of degrading the benzene series comprises, by mass, 16% -22% of styrene-acrylic emulsion, 5% -10% of organic siloxane modified polymer emulsion, 16% -21% of titanium dioxide, 20% -35% of triple superphosphate, 2% -5% of environment-friendly powder, 1% -2% of film-forming auxiliary agent, 0.05% -0.1% of pH regulator, 0.6% -1% of wetting dispersant, 0.3% -0.5% of cellulose, 0.1% -0.3% of defoaming agent, 0.6% -1% of preservative, 0.2% -0.3% of thickening agent and 15% -30% of water, wherein the environment-friendly powder is a compound of graphene oxide and titanium dioxide. The basic concept is as follows: the styrene-acrylic emulsion and the organic siloxane modified polymer emulsion are mixed, spliced and fused to realize function complementation, so that the coating has better water resistance and heat resistance while a perfect paint film is achieved; the environment-friendly powder which takes the compound of the graphene oxide and the titanium dioxide as the main component is added, so that the photocatalytic degradation of the benzene series is realized, the degradation is more efficient, and the effect is better; the coordination effect among all the components in the coating is fully exerted, so that the prepared coating has outstanding leveling property, glossiness and fullness, and meets the requirement of indoor coatings.

In order to further improve the capacity of photocatalytic degradation of benzene series by environment-friendly powder, the state and content of graphene oxide and titanium dioxide forming the environment-friendly powder are limited, wherein the graphene oxide is prepared by a Hummers method, the titanium dioxide is nano titanium dioxide prepared by a sol-gel method, and the mass ratio of the graphene oxide to the nano titanium dioxide is 1: 4-6.

The process parameters for preparing graphene oxide by the Hummers method and preparing nano titanium dioxide by the sol-gel method can be selected conventionally, and the method is not limited in the application and is exemplary: the method for preparing the graphene oxide by adopting the Hummers method comprises the following steps: filling a 250mL reaction bottle in an ice-water bath, adding 100mL concentrated sulfuric acid, and adding a solid mixture of 1-3g of graphite powder and 0.1-2g of sodium nitrate under stirring; adding 4-8g of potassium permanganate in several times, controlling the reaction temperature to be not more than 15-20 ℃, stirring for 2-2.5h, then heating to about 30-40 ℃, and continuing stirring for 20-40 min; slowly adding 100ml of deionized water, continuously stirring for 10-25min, and adding hydrogen peroxide to reduce residual oxidant to make the solution become bright yellow; filtering while hot, washing with 5% HCl solution and deionized water until no sulfate radical is detected in the filtrate, to obtain graphene oxide, and drying the filter cake in a vacuum drying oven at 60 deg.C.

The preparation method of graphene oxide in the following examples is as follows:

filling a 250mL reaction bottle in an ice-water bath, adding 100mL concentrated sulfuric acid, and adding a solid mixture of 2g of graphite powder and 1g of sodium nitrate under stirring; adding 6g of potassium permanganate in batches, controlling the reaction temperature to be not more than 15 ℃, stirring for reaction for 2 hours, then heating to about 35 ℃, and continuing stirring for 30 min; slowly adding 100ml of deionized water, continuously stirring for 20min, and adding hydrogen peroxide to reduce residual oxidant to make the solution bright yellow; and filtering while the solution is hot, and washing the solution by using a 5% HCl solution and deionized water until no sulfate radical is detected in the filtrate, thereby obtaining the graphene oxide.

The method for preparing the nano titanium dioxide by adopting the sol-gel method is as follows: mixing 40-55mL of butyl titanate and 10-15mL of absolute ethyl alcohol to prepare a solution A; mixing 40-50mL of absolute ethyl alcohol, 2-3mL of distilled water and 1.5-2mL of glacial acetic acid to prepare a solution B; magnetically stirring the solution A for 20-40min, pouring the solution B into a constant-pressure funnel to enable the solution B to be dripped into the solution A at the speed of 2-3 drops/s; and after the dripping is finished, stirring for 50-60 minutes, dripping 6-10 drops of triethylamine, stirring for 3-8 minutes, and enabling the solution to be oily after the stirring is finished. Drying the obtained gel in a vacuum drying oven at the temperature of 100-120 ℃, wherein the gel is changed into yellow crystals after drying for 20-40 min; grinding the yellow crystal into powder, then drying for 4-6h under the condition of 333K in a vacuum drying oven, standing for 9-12h in a muffle furnace at the temperature of 400-.

The preparation method of the nano titanium dioxide in the following examples is as follows:

mixing 50mL of butyl titanate and 12mL of absolute ethyl alcohol to prepare a solution A; taking 45mL of absolute ethyl alcohol, 2.5mL of distilled water and 2mL of glacial acetic acid, and mixing to prepare a solution B; magnetically stirring the solution A for 30min, pouring the solution B into a constant-pressure funnel to enable the solution B to be dripped into the solution A at the speed of 2-3 drops/s; stirring for 50 minutes after the dripping is finished, dripping 8 drops of triethylamine, stirring for 5 minutes again, and enabling the solution to be oily after the stirring is finished; drying the obtained oily gel in a vacuum drying oven at 110 deg.C for 30min to obtain yellow crystal; taking out the yellow crystal, pouring the yellow crystal into a grinding bowl, grinding the yellow crystal into powder, drying the powder for 5 hours in a vacuum drying oven under the condition of 333K, standing the powder for 10 hours in a muffle furnace at the temperature of 450 ℃, calcining the powder to obtain white powder, and drying the white powder to obtain the nano-scale titanium dioxide powder.

The infrared spectrogram of the prepared nano titanium dioxide is shown in figure 1.

The embodiment of the application also provides a preparation method of the environment-friendly powder, which comprises the following steps:

step A: mixing graphene oxide with ultrapure water, carrying out ultrasonic crushing for 20-30min, centrifuging at the rotating speed of 4000r/min for 10min, carrying out solid-liquid separation to obtain a graphene oxide solution, and heating the obtained graphene oxide solution to boiling for later use;

and B: mixing titanium dioxide and ultrapure water, carrying out ultrasonic crushing for 20-30min, carrying out solid-liquid separation to obtain a titanium dioxide solution, heating the titanium dioxide solution to 85-95 ℃, and adding the titanium dioxide solution into the boiling graphene oxide solution obtained in the step A within 25-35min to obtain a hydrolysate;

and C: heating the hydrolysate obtained in the step B to 150-160 ℃ at the speed of 0.8-1.2 ℃/min, and then carrying out hydrothermal reaction for 10-12 h; washing the obtained reaction product, drying for 20-30h in the environment of 75-85 ℃, calcining in the environment of 450-460 ℃ after grinding, and preserving heat for 2-2.5h to obtain the environment-friendly powder.

In order to make the obtained coating system more stable, have stronger wetting property and improve the dispersion efficiency of each component in the coating system, a water-soluble nonionic wetting agent is selected in the application, and the nonionic wetting agent X405 can be selected as an exemplary nonionic wetting agent.

In order to enable the foam breaking speed to be higher and the foam breaking effect to be more obvious in the preparation process of the coating, a mineral oil type defoaming agent is selected in the coating, and a molecular-level defoaming agent A10 of a new material company in Hechuan can be specifically selected.

In order to enable the coating system to have good stability and rheological property and improve the water separation and delamination phenomenon of the coating, an alkali swelling thickener is adopted, and particularly, an anionic alkali swelling thickener ASE60 in American Rohm and Haas chemistry can be selected.

The embodiment of the application also provides a preparation method of the indoor coating capable of degrading the benzene series, which specifically comprises the following steps:

s1: preparing raw materials according to the formula amount, sequentially adding cellulose, a pH regulator, a wetting dispersant, a film-forming assistant and a defoaming agent into 2/3-5/6 deionized water which is equivalent to the total amount of the deionized water, and stirring at the stirring speed of 300-600 r/min;

s2: adjusting the stirring speed to 600-;

s3: pulping the lacquer pulp obtained in the S2 for 30-40min at the stirring speed of 800-;

s4: and reducing the stirring speed to 800r/min for 600-.

The invention is further illustrated below in the following examples.

In the following embodiment, the titanium dioxide is selected from rutile type titanium dioxide R996 of Tetrapython;

the pH regulator is 2-amino-2-methyl-1-propanol;

the film-forming additive is Istmann alcohol ester twelve;

the cellulose is 250HBR hydroxyethyl cellulose;

the antiseptic is selected from the mildew and algae resistant antiseptic EPW of Torrel (Sol) of UK.

Example 1

The embodiment provides an indoor coating capable of degrading benzene series, which comprises the following components in percentage by mass: 16% of styrene-acrylic emulsion, 6% of organic siloxane modified polymer emulsion, 17% of titanium dioxide, 25% of heavy calcium carbonate, 4% of environment-friendly powder, 1.4% of film-forming additive, 0.07% of pH regulator, 0.7% of wetting dispersant, 0.4% of cellulose, 0.18% of defoaming agent, 0.7% of preservative, 0.25% of thickening agent and 28.93% of water, wherein the environment-friendly powder is a compound of graphene oxide and titanium dioxide.

The preparation method of the environment-friendly powder in the coating comprises the following steps:

step A: mixing graphene oxide and ultrapure water according to the proportion of 80: mixing the materials according to the proportion of 100, carrying out ultrasonic crushing for 20min, centrifuging for 10min at the rotating speed of 4000r/min, carrying out solid-liquid separation to obtain a graphene oxide solution, and heating the graphene oxide solution to boiling for later use;

and B: mixing titanium dioxide and ultrapure water according to the proportion of 80: mixing the materials according to the proportion of 100, carrying out ultrasonic crushing for 25min, centrifuging for 10min at the rotating speed of 4000r/min, carrying out solid-liquid separation to obtain a titanium dioxide solution, heating the obtained titanium dioxide solution to 95 ℃, adding the titanium dioxide solution into the boiling graphene oxide solution obtained in the step A within 25min to obtain a hydrolysate, and controlling the mass ratio of graphene oxide to titanium dioxide in the hydrolysate to be 1: 5;

and C: heating the hydrolysate obtained in the step B to 150 ℃ at the speed of 1.0 ℃/min, and then carrying out hydrothermal reaction for 10 h; washing and vacuum-filtering the obtained reaction product, drying the obtained filter cake for 28h in an environment of 80 ℃, grinding, calcining at 450 ℃, and preserving heat for 2h to obtain the environment-friendly powder.

The preparation method of the indoor coating capable of degrading the benzene series comprises the following steps:

s1: preparing raw materials according to the formula amount, sequentially adding cellulose, a pH regulator, a wetting dispersant, a film-forming assistant and a defoaming agent into 3/4 deionized water which is equivalent to the total amount of the deionized water, and stirring at the stirring speed of 450 r/min;

s2: adjusting the stirring speed to 800r/min, and sequentially adding titanium dioxide, environment-friendly powder and heavy calcium carbonate into the mixture obtained in S1 to obtain paint paste;

s3: pulping the lacquer pulp obtained in the step S2 for 35min at the stirring speed of 1000r/min, and adjusting the fineness of the lacquer pulp to be below 55 mu m;

s4: and (3) reducing the stirring speed to 700r/min, sequentially adding the rest deionized water, the styrene-acrylic emulsion, the organic siloxane modified polymer emulsion, the preservative and the thickening agent into the beaten paint slurry obtained in the step S3, and continuously stirring until the stormer viscosity of the paint obtained at 25 ℃ is 105KU, thus obtaining the indoor paint capable of degrading the benzene series.

Example 2

The embodiment provides an indoor coating capable of degrading benzene series, which comprises the following components in percentage by mass: 18% of styrene-acrylic emulsion, 8% of organic siloxane modified polymer emulsion, 19% of titanium dioxide, 30% of heavy calcium carbonate, 4.5% of environment-friendly powder, 1.8% of film-forming additive, 0.08% of pH regulator, 0.8% of wetting dispersant, 0.45% of cellulose, 0.24% of defoaming agent, 0.9% of preservative, 0.28% of thickening agent and 16.67% of water, wherein the environment-friendly powder is a compound of graphene oxide and titanium dioxide.

The preparation method of the environment-friendly powder in the coating comprises the following steps:

step A: mixing graphene oxide and ultrapure water according to the proportion of 80: 80, carrying out ultrasonic crushing for 30min, centrifuging for 10min at the rotating speed of 4000r/min, carrying out solid-liquid separation to obtain a graphene oxide solution, and heating the graphene oxide solution to boiling for later use;

and B: mixing titanium dioxide and ultrapure water according to the proportion of 80: mixing the materials according to the proportion of 100, carrying out ultrasonic crushing for 20min, centrifuging at the rotating speed of 4000r/min for 10min, carrying out solid-liquid separation to obtain a titanium dioxide solution, heating the obtained titanium dioxide solution to 90 ℃, adding the titanium dioxide solution into the boiling graphene oxide solution obtained in the step A within 30min to obtain a hydrolysate, and controlling the mass ratio of the graphene oxide to the titanium dioxide in the hydrolysate to be 1: 4;

and C: heating the hydrolysate obtained in the step B to 160 ℃ at the speed of 1.0 ℃/min, and then carrying out hydrothermal reaction for 12 h; washing and vacuum-filtering the obtained reaction product, drying the obtained filter cake for 24h in an environment of 80 ℃, grinding, calcining at 450 ℃, and preserving heat for 2h to obtain the environment-friendly powder.

The preparation method of the indoor coating capable of degrading the benzene series comprises the following steps:

s1: preparing raw materials according to the formula amount, sequentially adding cellulose, a pH regulator, a wetting dispersant, a film-forming assistant and a defoaming agent into 3/4 deionized water which is equivalent to the total amount of the deionized water, and stirring at the stirring speed of 450 r/min;

s2: adjusting the stirring speed to 800r/min, and sequentially adding titanium dioxide, environment-friendly powder and heavy calcium carbonate into the mixture obtained in S1 to obtain paint paste;

s3: pulping the lacquer pulp obtained in the step S2 for 35min at the stirring speed of 1000r/min, and adjusting the fineness of the lacquer pulp to be below 55 mu m;

s4: and (3) reducing the stirring speed to 700r/min, sequentially adding the rest deionized water, the styrene-acrylic emulsion, the organic siloxane modified polymer emulsion, the preservative and the thickening agent into the beaten paint slurry obtained in the step S3, and continuously stirring until the stormer viscosity of the paint obtained at 25 ℃ is 105KU, thus obtaining the indoor paint capable of degrading the benzene series.

Example 3

The embodiment provides an indoor coating capable of degrading benzene series, which comprises the following components in percentage by mass: 20% of styrene-acrylic emulsion, 10% of organic siloxane modified polymer emulsion, 16% of titanium dioxide, 28% of heavy calcium carbonate, 4% of environment-friendly powder, 1.5% of film-forming additive, 0.1% of pH regulator, 1% of wetting dispersant, 0.4% of cellulose, 0.15% of defoaming agent, 0.8% of preservative, 0.25% of thickening agent and 18.7% of water, wherein the environment-friendly powder is a compound of graphene oxide and titanium dioxide.

The preparation method of the environment-friendly powder in the coating comprises the following steps:

step A: mixing graphene oxide and ultrapure water according to the proportion of 80: mixing the materials according to the proportion of 100, carrying out ultrasonic crushing for 30min, centrifuging for 10min at the rotating speed of 4000r/min, carrying out solid-liquid separation to obtain a graphene oxide solution, and heating the graphene oxide solution to boiling for later use;

and B: mixing titanium dioxide and ultrapure water according to the proportion of 80: mixing the materials according to the proportion of 100, carrying out ultrasonic crushing for 30min, centrifuging for 10min at the rotating speed of 4000r/min, carrying out solid-liquid separation to obtain a titanium dioxide solution, heating the obtained titanium dioxide solution to 90 ℃, adding the titanium dioxide solution into the boiling graphene oxide solution obtained in the step A within 30min to obtain a hydrolysate, and controlling the mass ratio of graphene oxide to titanium dioxide in the hydrolysate to be 1: 6;

and C: heating the hydrolysate obtained in the step B to 150 ℃ at the speed of 1.0 ℃/min, and then carrying out hydrothermal reaction for 10 h; washing and vacuum-filtering the obtained reaction product, drying the obtained filter cake for 24h in an environment of 80 ℃, grinding, calcining at 460 ℃, and preserving heat for 2h to obtain the environment-friendly powder.

The preparation method of the indoor coating capable of degrading the benzene series comprises the following steps:

s1: preparing raw materials according to the formula amount, sequentially adding cellulose, a pH regulator, a wetting dispersant, a film-forming assistant and a defoaming agent into 3/4 deionized water which is equivalent to the total amount of the deionized water, and stirring at the stirring speed of 450 r/min;

s2: adjusting the stirring speed to 800r/min, and sequentially adding titanium dioxide, environment-friendly powder and heavy calcium carbonate into the mixture obtained in S1 to obtain paint paste;

s3: pulping the lacquer pulp obtained in the step S2 for 35min at the stirring speed of 1000r/min, and adjusting the fineness of the lacquer pulp to be below 55 mu m;

s4: and (3) reducing the stirring speed to 700r/min, sequentially adding the rest deionized water, the styrene-acrylic emulsion, the organic siloxane modified polymer emulsion, the preservative and the thickening agent into the beaten paint slurry obtained in the step S3, and continuously stirring until the stormer viscosity of the paint obtained at 25 ℃ is 110KU, thus obtaining the indoor paint capable of degrading the benzene series.

Comparative example 1

The embodiment provides an indoor coating capable of degrading benzene series, which comprises the following components in percentage by mass: 16% of styrene-acrylic emulsion, 6% of organic siloxane modified polymer emulsion, 17% of titanium dioxide, 25% of heavy calcium carbonate, 1.8% of nano titanium dioxide, 2.2% of graphene oxide, 1.4% of film-forming additive, 0.07% of pH regulator, 0.7% of wetting dispersant, 0.4% of cellulose, 0.18% of defoaming agent, 0.7% of preservative, 0.25% of thickening agent and 28.93% of water.

The preparation method of the indoor coating capable of degrading the benzene series comprises the following steps:

s1: preparing raw materials according to the formula amount, sequentially adding cellulose, a pH regulator, a wetting dispersant, a film-forming assistant and a defoaming agent into 3/4 deionized water which is equivalent to the total amount of the deionized water, and stirring at the stirring speed of 450 r/min;

s2: adjusting the stirring speed to 800r/min, and sequentially adding titanium dioxide, graphene oxide and heavy calcium carbonate into the mixture obtained in S1 to obtain paint paste;

s3: pulping the lacquer pulp obtained in the step S2 for 35min at the stirring speed of 1000r/min, and adjusting the fineness of the lacquer pulp to be below 55 mu m;

s4: and (3) reducing the stirring speed to 700r/min, sequentially adding the rest deionized water, the styrene-acrylic emulsion, the organic siloxane modified polymer emulsion, the preservative and the thickening agent into the beaten paint slurry obtained in the step S3, and continuously stirring until the stormer viscosity of the obtained paint is 105KU at 25 ℃, thus obtaining the indoor paint.

Comparative example 2

The comparative example provides an indoor paint which comprises the following components in percentage by mass: 16% of styrene-acrylic emulsion, 6% of organic siloxane modified polymer emulsion, 17% of titanium dioxide, 25% of heavy calcium carbonate, 1.4% of film-forming additive, 0.07% of pH regulator, 0.7% of wetting dispersant, 0.4% of cellulose, 0.18% of defoamer, 0.7% of preservative, 0.25% of thickener and 32.93% of water.

The preparation method of the indoor coating capable of degrading the benzene series comprises the following steps:

s1: preparing raw materials according to the formula amount, sequentially adding cellulose, a pH regulator, a wetting dispersant, a film-forming assistant and a defoaming agent into 3/4 deionized water which is equivalent to the total amount of the deionized water, and stirring at the stirring speed of 450 r/min;

s2: adjusting the stirring speed to 800r/min, and sequentially adding titanium dioxide and heavy calcium carbonate into the mixture obtained in S1 to obtain paint paste;

s3: pulping the lacquer pulp obtained in the step S2 for 35min at the stirring speed of 1000r/min, and adjusting the fineness of the lacquer pulp to be below 55 mu m;

s4: and (3) reducing the stirring speed to 700r/min, sequentially adding the rest deionized water, the styrene-acrylic emulsion, the organic siloxane modified polymer emulsion, the preservative and the thickening agent into the beaten paint slurry obtained in the step S3, and continuously stirring until the stormer viscosity of the obtained paint is 105KU at 25 ℃, thus obtaining the indoor paint.

Comparative example 3

The embodiment provides an indoor paint which comprises the following components in percentage by mass: 18% of styrene-acrylic emulsion, 8% of organic siloxane modified polymer emulsion, 19% of titanium dioxide, 30% of heavy calcium carbonate, 1.8% of film-forming additive, 0.08% of pH regulator, 0.8% of wetting dispersant, 0.4% of cellulose, 0.24% of defoaming agent, 0.9% of preservative, 0.28% of thickening agent and 21.22% of water, wherein the environment-friendly powder is a compound of graphene oxide and titanium dioxide.

The preparation method of the indoor coating comprises the following steps:

s1: preparing raw materials according to the formula amount, sequentially adding cellulose, a pH regulator, a wetting dispersant, a film-forming assistant and a defoaming agent into 3/4 deionized water which is equivalent to the total amount of the deionized water, and stirring at the stirring speed of 450 r/min;

s2: adjusting the stirring speed to 800r/min, and sequentially adding titanium dioxide and heavy calcium carbonate into the mixture obtained in S1 to obtain paint paste;

s3: pulping the lacquer pulp obtained in the step S2 for 35min at the stirring speed of 1000r/min, and adjusting the fineness of the lacquer pulp to be below 55 mu m;

s4: and (3) reducing the stirring speed to 700r/min, sequentially adding the rest deionized water, the styrene-acrylic emulsion, the organic siloxane modified polymer emulsion, the preservative and the thickening agent into the beaten paint slurry obtained in the step S3, and continuously stirring until the stormer viscosity of the obtained paint is 105KU at 25 ℃, thus obtaining the indoor paint.

Example of detection

The performances of the coatings obtained in examples 1-3 and comparative examples 1-3 in degrading benzene series are detected, and the specific scheme is as follows:

(1) a standard curve of benzene content was plotted:

respectively measuring 2.75 muL, 5.5 muL, 11 muL, 16.5 muL and 22.5 muL of analytically pure benzene into 5 250mL of dry and clean conical flasks, respectively marking the triangular flasks as 1, 2, 3, 4 and 5 according to the content, sealing the triangular flask mouths by using preservative films, adhesive tapes and air bags, placing the triangular flasks in a 100 ℃ oven for baking for 10min until the benzene is completely vaporized, taking out the triangular flasks, cooling the triangular flasks to room temperature to serve as a benzene gas standard sample, taking 5mL (from small to large according to concentration) of the benzene gas standard sample by using a sample injection needle, injecting the benzene gas standard sample into a gas chromatograph, operating for 6min to obtain a spectrogram and data, and finishing the data to prepare a working curve. Wherein the data of the benzene gas standard sample is shown in Table 1, and the comparison table of the benzene gas concentration is shown in Table 2:

table 1 benzene standard sample data

Serial number	Pure reagent amount (V1)	ABenzene and its derivatives
			1	2.75μL	2358.274
2	5.5μL	5461.709
			3	11μL	1.54×104
4	16.5μL	1.61×104
			5	22.5μL	2.45×104

The average density of benzene was: rho is 0.88 g/mL; v_{General assembly}＝250mL；

The concentration of each benzene standard was calculated according to the following formula:

density x volume/total volume rho x V₁/V_{General assembly}；

TABLE 2 comparison of benzene concentration

(2) Taking the peak area as the abscissa and the benzene concentration as the ordinate to make a standard curve: the resulting curve is shown in FIG. 2: the equation for the standard curve in fig. 2 is: y is 2.53+0.0031391X

(3) Experimental data and results

The coatings prepared in examples 1-3 and comparative examples 1-3 were applied in a closed room with a high benzene content, and 5ml of air was injected every two days using a gas chromatography standard injection needle to obtain the peak area of benzene.

And (3) according to a standard curve equation, the peak area value is obtained: y2.53 +0.0031391X, the corresponding benzene concentration was calculated, where the peak area and benzene concentration were unchanged in the experimental groups corresponding to comparative examples 2 and 3, and the experimental data for the coatings obtained in examples 1-3 and comparative example 1 are shown in table 3:

TABLE 3 photo catalytic oxidation gas phase detection data table for benzene

The experimental results of the comparative examples 1 to 3 and the comparative examples 2 and 3 show that in the experiment of catalytic oxidation of benzene, the peak area and the concentration of benzene rapidly decrease in 4 days after the construction of the coating obtained in the examples 1 to 3, the peak area and the concentration of benzene decrease gradually and gradually decrease with the increase of the reaction time until the coating reaches equilibrium, and the catalytic degradation rate of benzene is more than or equal to 96.08% after sixteen days of the construction, thereby demonstrating that the indoor coating capable of degrading benzene series provided by the application can effectively degrade benzene series in the air.

The experimental results of comparative examples 1-3 and comparative example 1 show that the prepared environment-friendly powder can further improve the degradation efficiency of the coating on benzene series in air and improve the degradation effect by compounding the graphene oxide and the nano titanium dioxide.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.