CN116333518B

CN116333518B - Wear-resistant paint capable of releasing anions and preparation method thereof

Info

Publication number: CN116333518B
Application number: CN202310129231.1A
Authority: CN
Inventors: 邓科洹; 孙大东
Original assignee: Changzhou Tianrui New Material Technology Co ltd
Current assignee: Changzhou Tianrui New Material Technology Co ltd
Priority date: 2023-02-17
Filing date: 2023-02-17
Publication date: 2023-09-05
Anticipated expiration: 2043-02-17
Also published as: CN116333518A

Abstract

The invention relates to an anion-releasing wear-resistant coating and a preparation method thereof, belonging to the technical field of coating compositions. The coating comprises the following components in parts by weight: 50-70 parts of heavy calcium carbonate, 10-16 parts of seaweed mud, 6-8 parts of cast stone powder, 6.5-9 parts of negative ion generating agent, 1.2-1.8 parts of carboxyl cellulose and 1.5-2 parts of redispersible rubber powder; wherein, the anion generator takes tourmaline powder as a core, forms a porous cerium and zirconium oxide coating structure through chelating adsorption, conversion roasting decomposition, has good water retention and photocatalysis, and is assisted with seaweed mud to improve the hygroscopicity and air permeability of the coating, thereby being beneficial to the generation and release of anions, and the release amount of anions of the coating reaches 2216-2374 per cm after detection ³ Reaching the standard of high-quality fresh air.

Description

Wear-resistant paint capable of releasing anions and preparation method thereof

Technical Field

The invention belongs to the technical field of coating compositions, and particularly relates to an anion-releasing wear-resistant coating and a preparation method thereof.

Background

Along with the rapid improvement of living standard, environmental pollution is more serious, nature and health have become unprecedented pursuits, people put forward new imagination and new requirements for houses closely related to their daily lives, pursuit of healthy, green and comfortable houses has become a basic wish of people's life. Healthy, green residential space is a life style that is embodied in residential and residential environments and living behavior, and includes not only physical quantities associated with living, such as temperature, humidity, ventilation, noise, light, and air quality, wherein the concentration of negative ions in the air is listed as an important parameter for measuring the quality of the air; the research of scholars shows that the negative ions have promotion effects on a plurality of systems in animals, have inhibition and auxiliary treatment effects on more than about 30 diseases, and particularly have remarkable functions in the field of biological research and health care functions, so that the negative ions are called as 'air vitamins' in medicine.

There are many methods for generating negative ions in daily life, such as turning liquid water into gaseous water by ultrasonic generation of wafers, in which process negative ions are generated by atomization; in industry, alternating voltage is converted into ultrahigh direct voltage, and then negative ions are generated by electrolyzing air through tip discharge; various rays and lightning in natural phenomenaThe principle of ionization of the atmosphere to generate negative ions is similar to that of tip discharge, such as storm and the like; the photosynthesis of plants and the tip discharge of the tree tops can be combined to generate photoelectric effect under certain conditions, and negative ions are generated by ionizing air; the water molecules in the waterfall fall from the mountain top can run at high speed under the action of gravity so as to generate cracking and gasification to generate negative ions; in the research process of negative ions, the tourmaline is found to have a permanent electrode, can generate static electricity of megaelectron volts, can electrolyze air to generate negative ions, thereby initiating the climax of the research of negative ion powder, and further providing a series of negative ion products, mainly comprising negative ion ceramics, negative ion paint, negative ion textiles and the like; however, these anion generating products have low anion release amounts, and it is generally difficult or impossible to achieve 1500 ions/cm ³ Standard for fresh air.

Disclosure of Invention

In order to solve the technical problems in the background art, the invention aims to provide an anion-releasing wear-resistant coating and a preparation method thereof.

The aim of the invention can be achieved by the following technical scheme:

an anion releasing wear-resistant coating comprises the following components in parts by weight:

50-70 parts of heavy calcium carbonate, 10-16 parts of seaweed mud, 6-8 parts of cast stone powder, 6.5-9 parts of negative ion generating agent, 1.2-1.8 parts of carboxyl cellulose and 1.5-2 parts of redispersible rubber powder;

the negative ion generator is prepared by the following method:

step A1: mixing a silane coupling agent KH580 and an ethanol solution under the protection of nitrogen, regulating the pH value to 4.5-5.0, stirring and hydrolyzing at room temperature, adding superfine tourmaline powder, performing ultrasonic dispersion, slowly regulating the pH value to be neutral in a stirring state, controlling the overall dispersion coupling time to be 3-4h, condensing the silane coupling agent KH580 with tourmaline powder after hydrolysis, grafting sulfur-containing groups on the surface of the silane coupling agent KH580, centrifuging, taking out precipitate, and drying to prepare coupling functional micro powder;

further, the usage ratio of the superfine tourmaline powder, the silane coupling agent KH580 and the ethanol solution is 50g:2.4-2.8mL:200-250mL, the concentration of ethanol solution is 35%, and the hydrolysis time is 40-60min.

Step A2: dispersing coupling functional micro powder in deionized water to form uniform suspension, slowly adding ferric chloride solution under high-speed stirring, standing and aging for 12 hours at room temperature, chelating sulfur-containing groups grafted on the surface of the coupling functional micro powder with ferric iron, enriching ferric iron on the surface layer, removing supernatant, taking precipitate, and press-filtering to prepare the iron-rich functional micro powder;

further, the dosage ratio of the coupling functional micro powder, the ferric chloride solution and the deionized water is 50g:8-10mL:140-160mL, and the concentration of ferric chloride solution is 20%.

Step A3: mixing the iron-rich functional micro powder with deionized water, heating to 55-65 ℃, applying 20kHz ultrasonic dispersion, simultaneously dropwise adding ammonia water to adjust the pH value to 8.0-8.5, primarily hydrolyzing ferric iron on the surface layer of the iron-rich functional micro powder to form microgel, then adding a solution of cerium chloride and zirconium nitrate, setting the stirring speed to 300-350rpm, continuously heating to 88-95 ℃, slowly dropwise adding sodium hydroxide solution to the pH value of 10.0, standing for 3-4h, filtering the reaction solution, taking a filter cake, washing and drying to prepare a composite precursor;

further, the dosage ratio of the iron-rich functional micro powder, the cerium chloride, the zirconium nitrate and the deionized water is 50g:1.7-2.5g:0.3-0.5g:180-220mL, the concentration of ammonia water is 8%, and the concentration of sodium hydroxide solution is 4.5%.

Step A4: drying the composite precursor at 120-150 ℃ for 30-40min, heating to 550-580 ℃ for heat preservation and roasting for 1.5-2h, heating to 850-880 ℃ for heat preservation and roasting for 1.2-1.6h, cooling and scattering to prepare the negative ion generator.

A preparation method of anion release wear-resistant paint comprises the following steps:

step S1: uniformly mixing heavy calcium carbonate, seaweed mud, cast stone powder, negative ion generator, carboxyl cellulose and redispersible rubber powder to prepare composite powder;

step S2: and (3) stirring and mixing the composite powder and water according to the powder-water ratio of 1:0.42-0.48 to prepare the anion-releasing wear-resistant coating.

The invention has the beneficial effects that:

the invention prepares a negative ion generating agent, which takes tourmaline powder with the function of releasing negative ions as a raw material, grafts sulfur-containing groups on the surface through silane coupling agent KH580 treatment, then enriches ferric iron on the surface through chelation, forms microgel with adsorption effect on the surface through hydrolysis of the ferric iron, captures cerium and zirconium ions, converts hydroxide with micro-nano structure in alkaline environment to be attached on the surface of tourmaline particles, and forms porous cerium and zirconium oxide coating tourmaline structure through roasting decomposition and carbonization, wherein porous cerium and zirconium oxidation has good water retention and photocatalysis effects, and can effectively catalyze tourmaline to generate negative ions; according to the invention, seaweed mud is added for compounding, so that the coating has certain hygroscopicity and air permeability, is favorable for generating and releasing negative ions, and is assisted with cast stone powder and redispersible rubber powder, so that the film forming property and the film wear resistance of the coating are ensured; through detection, the release amount of negative ions of the paint for 48 hours reaches 2216-2374 per cm ³ Compared with the existing tourmaline doped paint, the paint has excellent negative ion release capacity, adopts Ding Nibu to simulate clothes wiping, and has abrasion loss of only 27-49mg/cm after 100 times of friction ² Has good wear resistance and is suitable for indoor decoration.

Detailed Description

The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

Example 1

The preparation method of the anion release wear-resistant paint specifically comprises the following steps:

1. preparation of anion generating agent

A1, mixing a silane coupling agent KH580 and an ethanol solution with the concentration of 35% under the protection of nitrogen, adding hydrochloric acid to adjust the pH value to 4.5, stirring and hydrolyzing for 40min by using 120rpm, adding superfine tourmaline powder (selected from the fineness of 2000 meshes) into the hydrolyzed solution, performing ultrasonic dispersion for 20min at 33kHz, then applying 300rpm to stir, slowly dropwise adding ammonia water to adjust the pH value to be neutral, controlling the overall dispersion coupling time to be 3h, and controlling the dosage ratio of the superfine tourmaline powder, the silane coupling agent KH580 and the ethanol solution to be 50g in the reaction: 2.8mL:250mL, centrifuging, taking precipitate, drying, and preparing into coupling functional micro powder;

a2, taking coupling function micro powder and deionized water, performing ultrasonic dispersion for 10min at 33kHz to form uniform suspension, then applying high-speed stirring at 800rpm, slowly dripping 20% ferric chloride solution into the suspension within 40min, standing and aging for 12h at room temperature, and controlling the dosage ratio of the coupling function micro powder, the ferric chloride solution and the deionized water to be 50g in the reaction: 10mL:160mL, removing supernatant after reaction, taking precipitation and filter pressing to prepare iron-rich functional micro powder;

a3, mixing the iron-rich functional micro powder and deionized water, heating to 65 ℃, applying 20kHz ultrasonic dispersion, simultaneously dropwise adding 8% ammonia water to adjust the pH value to 8.5, mixing cerium chloride and zirconium nitrate, dissolving into a saturated solution, adding the saturated solution into the mixed solution, stirring at 350rpm, continuously heating to 95 ℃, slowly dropwise adding 4.5% sodium hydroxide solution to the pH value of 10.0, standing for 3h, and controlling the dosage ratio of the iron-rich functional micro powder, the cerium chloride, the zirconium nitrate and the deionized water to 50g in the reaction: 1.7g:0.5g:220mL, filtering the reaction solution, and washing and drying a filter cake to prepare a composite precursor;

and A4, placing the composite precursor in a muffle furnace, drying at 150 ℃ for 30min, heating to 580 ℃ for heat preservation and roasting for 1.5h, heating to 880 ℃ for heat preservation and roasting for 1.2h, cooling, and scattering to prepare the negative ion generator.

2. Preparation of anion releasing wear-resistant paint

S1, taking the following raw materials in parts by weight: 70 parts of heavy calcium carbonate, 10 parts of seaweed mud, 8 parts of cast stone powder, 6.5 parts of negative ion generator, 1.8 parts of carboxyl cellulose and 1.5 parts of redispersible rubber powder, and the above materials are added into a mixer to be uniformly mixed to prepare composite powder;

s2, adding water into the composite powder according to the powder-water ratio of 1:0.48, and stirring and mixing uniformly to prepare the negative ion release wear-resistant coating.

Example 2

1. preparation of anion generating agent

A1, mixing a silane coupling agent KH580 and an ethanol solution with the concentration of 35% under the protection of nitrogen, adding hydrochloric acid to adjust the pH value to 5.0, stirring and hydrolyzing for 60min at 120rpm, adding superfine tourmaline powder into the hydrolyzed solution, performing ultrasonic dispersion for 20min at 33kHz, then applying 300rpm to stir, slowly dropwise adding ammonia water to adjust the pH value to be neutral, controlling the overall dispersion coupling time to be 4h, and controlling the dosage ratio of the superfine tourmaline powder, the silane coupling agent KH580 and the ethanol solution to be 50g in the reaction: 2.4mL:200mL, centrifuging, taking precipitate, drying, and preparing into coupling function micropowder;

a2, taking coupling function micro powder and deionized water, performing ultrasonic dispersion for 10min at 33kHz to form uniform suspension, then applying high-speed stirring at 800rpm, slowly dripping 20% ferric chloride solution into the suspension within 50min, standing and aging for 12h at room temperature, and controlling the dosage ratio of the coupling function micro powder, the ferric chloride solution and the deionized water to be 50g in the reaction: 8mL:140mL, removing supernatant after reaction, taking precipitation and filter pressing to prepare iron-rich functional micro powder;

a3, mixing the iron-rich functional micro powder with deionized water, heating to 55 ℃, applying 20kHz ultrasonic dispersion, simultaneously dropwise adding 8% ammonia water to adjust the pH value to 8.0, mixing cerium chloride and zirconium nitrate, dissolving into a saturated solution, adding the saturated solution into the mixed solution, stirring at 300rpm, continuously heating to 88 ℃, slowly dropwise adding 4.5% sodium hydroxide solution to the pH value of 10.0, standing for 4 hours, and controlling the dosage ratio of the iron-rich functional micro powder, the cerium chloride, the zirconium nitrate and the deionized water to 50g in the reaction: 2.5g:0.3g:180mL, filtering the reaction solution, washing and drying a filter cake to prepare a composite precursor;

and A4, placing the composite precursor in a muffle furnace, drying at 120 ℃ for 40min, heating to 550 ℃ for heat preservation and roasting for 2h, heating to 850 ℃ for heat preservation and roasting for 1.6h, cooling, and scattering to prepare the negative ion generator.

2. Preparation of anion releasing wear-resistant paint

S1, taking the following raw materials in parts by weight: 50 parts of heavy calcium carbonate, 16 parts of seaweed mud, 6 parts of cast stone powder, 9 parts of negative ion generating agent, 1.2 parts of carboxyl cellulose and 2 parts of redispersible rubber powder, and adding the above materials into a mixer for uniformly mixing to prepare composite powder;

s2, adding water into the composite powder according to the powder-water ratio of 1:0.42, and stirring and mixing uniformly to prepare the negative ion release wear-resistant coating.

Example 3

1. preparation of anion generating agent

A1, mixing a silane coupling agent KH580 and an ethanol solution with the concentration of 35% under the protection of nitrogen, adding hydrochloric acid to adjust the pH value to 5.0, stirring and hydrolyzing for 55min at 120rpm, adding superfine tourmaline powder into the hydrolyzed solution, performing ultrasonic dispersion for 20min at 33kHz, then applying 300rpm to stir, slowly dropwise adding ammonia water to adjust the pH value to be neutral, controlling the overall dispersion coupling time to be 4h, and controlling the dosage ratio of the superfine tourmaline powder, the silane coupling agent KH580 and the ethanol solution to be 50g in the reaction: 2.6mL:220mL, centrifuging, taking precipitate, drying, and preparing into coupling function micropowder;

a2, taking coupling function micro powder and deionized water, performing ultrasonic dispersion for 10min at 33kHz to form uniform suspension, then applying high-speed stirring at 800rpm, slowly dripping 20% ferric chloride solution into the suspension within 50min, standing and aging for 12h at room temperature, and controlling the dosage ratio of the coupling function micro powder, the ferric chloride solution and the deionized water to be 50g in the reaction: 9mL:160mL, removing supernatant after reaction, taking precipitation and filter pressing to prepare iron-rich functional micro powder;

a3, mixing the iron-rich functional micro powder and deionized water, heating to 62 ℃, applying 20kHz ultrasonic dispersion, simultaneously dropwise adding 8% ammonia water to adjust the pH value to 8.0, mixing cerium chloride and zirconium nitrate, dissolving into a saturated solution, adding the saturated solution into the mixed solution, stirring at 350rpm, continuously heating to 90 ℃, slowly dropwise adding 4.5% sodium hydroxide solution to the pH value of 10.0, standing for 3.5h, and controlling the dosage ratio of the iron-rich functional micro powder to the cerium chloride to the zirconium nitrate to the deionized water to be 50g in the reaction: 2.1g:0.4g: filtering the reaction solution by 200mL, and washing and drying a filter cake to prepare a composite precursor;

and A4, placing the composite precursor in a muffle furnace, drying at 130 ℃ for 35min, heating to 560 ℃ for heat preservation and roasting for 1.8h, heating to 860 ℃ for heat preservation and roasting for 1.5h, cooling, and scattering to prepare the negative ion generating agent.

2. Preparation of anion releasing wear-resistant paint

S1, taking the following raw materials in parts by weight: 60 parts of heavy calcium carbonate, 14 parts of seaweed mud, 7 parts of cast stone powder, 8 parts of negative ion generating agent, 1.5 parts of carboxyl cellulose and 1.8 parts of redispersible rubber powder, and adding the above materials into a mixer for uniformly mixing to prepare composite powder;

s2, adding water into the composite powder according to the powder-water ratio of 1:0.45, and stirring and mixing uniformly to prepare the negative ion release wear-resistant coating.

Example 4

1. preparation of anion generating agent

A1, mixing a silane coupling agent KH580 and an ethanol solution with the concentration of 35% under the protection of nitrogen, adding hydrochloric acid to adjust the pH value to 5.0, stirring and hydrolyzing for 60min at 120rpm, adding superfine tourmaline powder into the hydrolyzed solution, performing ultrasonic dispersion for 20min at 33kHz, then applying 300rpm to stir, slowly dropwise adding ammonia water to adjust the pH value to be neutral, controlling the overall dispersion coupling time to be 3.5h, and controlling the dosage ratio of the superfine tourmaline powder, the silane coupling agent KH580 and the ethanol solution to be 50g in the reaction: 2.6mL:240mL, centrifuging, taking precipitate, drying, and preparing into coupling function micropowder;

a2, taking coupling function micro powder and deionized water, performing ultrasonic dispersion for 10min at 33kHz to form uniform suspension, then applying high-speed stirring at 800rpm, slowly dripping 20% ferric chloride solution into the suspension within 45min, standing and aging for 12h at room temperature, and controlling the dosage ratio of the coupling function micro powder, the ferric chloride solution and the deionized water to be 50g in the reaction: 8mL:160mL, removing supernatant after reaction, taking precipitation and filter pressing to prepare iron-rich functional micro powder;

a3, mixing the iron-rich functional micro powder and deionized water, heating to 62 ℃, applying 20kHz ultrasonic dispersion, simultaneously dropwise adding 8% ammonia water to adjust the pH value to 8.0, mixing cerium chloride and zirconium nitrate, dissolving into a saturated solution, adding the saturated solution into the mixed solution, stirring at 350rpm, continuously heating to 92 ℃, slowly dropwise adding 4.5% sodium hydroxide solution to the pH value of 10.0, standing for 3.6h, and controlling the dosage ratio of the iron-rich functional micro powder to the cerium chloride to the zirconium nitrate to the deionized water to be 50g in the reaction: 2.2g:0.38g:210mL, filtering the reaction solution, and washing and drying a filter cake to prepare a composite precursor;

and A4, placing the composite precursor in a muffle furnace, drying at 150 ℃ for 35min, heating to 580 ℃ for heat preservation and roasting for 1.6h, heating to 860 ℃ for heat preservation and roasting for 1.4h, cooling, and scattering to prepare the negative ion generator.

2. Preparation of anion releasing wear-resistant paint

S1, taking the following raw materials in parts by weight: 65 parts of heavy calcium carbonate, 15 parts of seaweed mud, 6.5 parts of cast stone powder, 7.5 parts of negative ion generator, 1.4 parts of carboxyl cellulose and 1.6 parts of redispersible rubber powder are added into a mixer to be uniformly mixed to prepare composite powder;

s2, adding water into the composite powder according to the powder-water ratio of 1:0.46, and stirring and mixing uniformly to prepare the negative ion release wear-resistant coating.

Comparative example

This comparative example was carried out in the same manner as in example 3, except that the negative ion generating agent was replaced with the same amount of tourmaline powder, and the remainder was the same.

The negative ion-releasing abrasion-resistant paint prepared in examples 1 to 4 and comparative example was applied onto the surface of a cement mortar board having a specification of 200X 10mm by blade coating, and the blade coating amount was controlled to be 1.6g/cm ² Curing for 24 hours in a constant temperature chamber with the temperature of 30 ℃ and the humidity of 85%, then placing in an acrylic sealing box with the side length of 1000mm, continuously standing for 48 hours in the constant temperature chamber, and detecting the negative ion content by adopting a DLY-6A232 atmospheric negative ion measuring instrument;

the cement mortar board with the negative ion wear-resistant paint released by the knife coating is maintained in a constant temperature chamber for 7d, then naturally maintained for 28d, and a multifunctional InnovenaBREX finger wear testing machine is adopted, ding Nibu is used as a friction material for carrying out wear resistance test, and the wear amount after 100 times of friction is measured and calculated;

the specific tests are shown in table 1:

TABLE 1

As can be seen from the data in Table 1, the anion release wear-resistant paint prepared by the invention has the anion release amount reaching 2216-2374 per cm in 48 hours ³ Shows excellent negative ion release function, adopts Ding Nibu to simulate clothes wiping, and has abrasion loss of only 27-49mg/cm after 100 times of friction ² Has good wear resistance and is suitable for indoor decoration.

In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.

Claims

1. An anion releasing wear resistant coating, comprising by weight:

the negative ion generator is prepared by the following method:

step A1: mixing a silane coupling agent KH580 and an ethanol solution under the protection of nitrogen, regulating the pH value to 4.5-5.0, stirring at room temperature for hydrolysis, adding superfine tourmaline powder for ultrasonic dispersion, slowly regulating the pH value to be neutral in a stirring state, controlling the overall dispersion coupling time to be 3-4h, centrifuging, taking out the precipitate, and drying to prepare coupling functional micro powder;

step A2: dispersing coupling functional micro powder in deionized water by ultrasonic, slowly adding ferric chloride solution under high-speed stirring, standing and aging for 12 hours at room temperature, removing supernatant, taking precipitate, and press-filtering to obtain iron-rich functional micro powder;

step A3: mixing the iron-rich functional micro powder with deionized water, heating to 55-65 ℃, applying 20kHz ultrasonic dispersion, simultaneously dropwise adding ammonia water to adjust the pH value to 8.0-8.5, then adding the solution of cerium chloride and zirconium nitrate, stirring, continuously heating to 88-95 ℃, slowly dropwise adding sodium hydroxide solution to the pH value of 10.0, standing for 3-4h, carrying out suction filtration on the reaction solution, taking a filter cake, washing and drying to prepare a composite precursor;

2. The anion releasing wear-resistant paint as claimed in claim 1, wherein the ratio of the amount of the ultrafine tourmaline powder, the silane coupling agent KH580 and the ethanol solution is 50g:2.4-2.8mL:200-250mL.

3. The anion releasing wear-resistant paint as claimed in claim 2, wherein the concentration of the ethanol solution is 35%, and the hydrolysis time is 40-60min.

4. The anion releasing wear-resistant paint as claimed in claim 3, wherein the coupling functional micro powder, ferric chloride solution and deionized water in the amount ratio of step A2 is 50g:8-10mL:140-160mL, and the concentration of ferric chloride solution is 20%.

5. The anion releasing wear-resistant paint as claimed in claim 4, wherein the dosage ratio of the iron-rich functional micro powder, cerium chloride, zirconium nitrate and deionized water in the step A3 is 50g:1.7-2.5g:0.3-0.5g:180-220mL.

6. The anion releasing wear-resistant paint of claim 5, wherein the concentration of ammonia water is 8%, and the concentration of sodium hydroxide solution is 4.5%.

7. A method for preparing the anion-releasing wear-resistant paint, which is used for preparing the anion-releasing wear-resistant paint according to any one of claims 1 to 6, and is characterized by comprising the following steps:

step S2: and (3) stirring and mixing the composite powder with water to prepare the anion-releasing wear-resistant coating.

8. The method for preparing the anion-releasing wear-resistant paint as claimed in claim 7, wherein the powder-water ratio of the composite powder to water is 1:0.42-0.48.