A preparation method of an artificial stone coating

Abstract

The present invention relates to the technical field of interior decoration, and specifically discloses a preparation method of an artificial stone coating. First, [VBIM][Cl] is prepared, and then the crosslinking agent IL is prepared; [VBIM][Cl] is added to methanol and stirred, with a solid content of 40-70 wt%, the crosslinking agent IL is added, and 1-5 wt% of a photoinitiator is added while stirring, and then it is loaded on an inert carrier, and a PILs coating is prepared by ultraviolet light irradiation; [BMIM][BF4] with a volume content of 10-80% is ultrasonically dispersed in methanol, then brushed on the PILs coating and infiltrated, and a hydrophilic artificial stone coating is prepared by water washing; or [BMIM][PF6] with a volume content of 10-80% is ultrasonically dispersed in methanol, then brushed on the PILs coating and infiltrated, and a hydrophobic artificial stone coating is prepared by water washing, achieving the effects of anti-fouling and moisture-proof of the artificial stone coating.

Description

Technical Field

[0001] The present invention relates to the technical field of interior decoration, and particularly relates to a preparation method of an artificial stone coating. Background Art

[0002] In the building materials field, coatings with self-cleaning ability are mainly divided into "hydrophobic self-cleaning coatings" with high contact angle and low surface energy, "hydrophilic self-cleaning coatings" with low contact angle and high surface energy, and photocatalytic self-cleaning coatings with titanium dioxide as a filler. The molecules constituting the hydrophobic self-cleaning coating are large in volume, low in cohesive energy density, and small in intermolecular force, so the surface energy is very low, and it has good hydrophobicity. The contact angle between the coating and water is large, and it has no adhesiveness to water molecules. It can carry away the attached pollutants through the rolling of surface water droplets and has good self-cleaning performance for the dust attached to the surface. The hydrophilic self-cleaning coating is the opposite of the hydrophobic self-cleaning coating. The surface energy of the coating is very high, and it has good hydrophilicity. The contact angle with water is small, and it has a strong affinity for water molecules. When the water droplet contacts the coating surface, it quickly spreads to form a water film and carries away the attached pollutants on the surface through the action of gravity, thereby achieving the self-cleaning effect. The preparation of the photocatalytic self-cleaning coating is mainly due to the surface oxygen vacancy defects caused by the lattice distortion of TiO2, which can produce good photocatalytic properties and superhydrophilicity under the action of (ultraviolet) light energy. The attached organic matter is finally oxidized into inorganic small molecules such as CO2 and H2O, and then using its superhydrophilic property, the water droplets spread on the coating surface and wash away the attached pollutants by relying on the action of gravity, thereby achieving the self-cleaning effect.

[0003] However, traditional anti-fouling or self-cleaning coatings can only have a single surface property. The exhaust gas discharged from cars and factories in cities and industrial areas contains oil, and the pollutants are mainly haze, oily smoke, industrial waste gas, automobile exhaust, and acid rain, which are suitable for hydrophilic self-cleaning coatings; in less industrialized areas, tourist cities, towns, etc., the pollutants are mainly hydrophilic dust pollution, so hydrophobic self-cleaning coatings need to be used. The use scenarios of coatings with a single surface property are limited and lack adjustability. And currently, the existing methods for regulating the surface hydrophilicity and hydrophobicity either rely on a complex chemical environment or require external energy stimulation to change the properties. The material and equipment costs are high, the process is complex, and the treatment time is long.

[0004] Therefore, there is an urgent need to provide a preparation method of an artificial stone coating, so as to prepare PILs coatings with different hydrophilic and hydrophobic surface properties, which can enhance or reduce the affinity of the coating for water droplets according to different usage environments, so as to achieve the effects of anti-fouling and moisture-proof respectively. Summary of the Invention

[0005] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. For this purpose, the present invention provides a preparation method of an artificial stone coating, so as to prepare PILs coatings with different hydrophilic and hydrophobic surface properties, which can enhance or reduce the affinity of the coating for water droplets according to different use environments, so as to achieve the effects of anti-fouling and moisture-proof respectively.

[0006] The first aspect of the present invention provides a preparation method of an artificial stone coating.

[0007] Specifically, it includes the following steps:

[0008] (1) First, add 1-vinylimidazole and 1-chlorobutane, then add hydroquinone and heat. After cooling, dissolve it with dichloromethane, and then add it to anhydrous ether and stir to obtain [VBIM][Cl];

[0009] (2) Add 1-vinylimidazole and dichloride, then add hydroquinone and heat. After cooling, dissolve it with dichloromethane, and then add it to anhydrous ether and stir to obtain a cross-linking agent IL;

[0010] (3) Add [VBIM][Cl] to methanol (MeOH) and stir. The solid content is 40-70 wt%, add the cross-linking agent IL, add 1-5 wt% of a photoinitiator while stirring, and then load it on an inert carrier, and irradiate it with ultraviolet light to obtain a PILs coating;

[0011] (4) Ultrasonically disperse 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMPF4) with a volume content of 10-80% in methanol (MeOH), then brush it on the PILs coating for infiltration, and wash it with water to obtain a hydrophilic artificial stone coating; or ultrasonically disperse 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6) with a volume content of 10-80% in methanol (MeOH), then brush it on the PILs coating for infiltration, and wash it with water to obtain a hydrophobic artificial stone coating;

[0012] In step (2), the dichloride is any one of 1,4-dichlorobutane, 1,6-dichlorohexane, and 1,8-dichlorooctane.

[0013] Preferably, in step (1), the molar ratio of 1-vinylimidazole to 1-chlorobutane is 1-1.3:1.

[0014] More preferably, the molar ratio of 1-vinylimidazole to 1-chlorobutane is 1.2:1.

[0015] Preferably, in step (1), the heating temperature is 40-80 °C and the time is 12-48 h.

[0016] Further preferably, in step (1), the heating is carried out in an oven, and the temperature control program of the oven is as follows: (a) heating process: heating to 60 °C at a heating rate of 1-10 °C / min; (b) constant temperature process: maintaining at 60 °C for 24 h.

[0017] Preferably, in step (2), the molar ratio of 1-vinylimidazole to the dichloride is 2-2.3:1.

[0018] Further preferably, the molar ratio of 1-vinylimidazole to the dichloride is 2.2:1.

[0019] Preferably, in step (2), 1-vinylimidazole and 1,4-dichlorobutane are added, then hydroquinone is added for heating. After cooling, it is dissolved in dichloromethane, and then added to anhydrous ether and stirred to obtain the crosslinking agent IL-4.

[0020] Preferably, in step (2), 1-vinylimidazole and 1,6-dichlorohexane are added, then hydroquinone is added for heating. After cooling, it is dissolved in dichloromethane, and then added to anhydrous ether and stirred to obtain the crosslinking agent IL-6.

[0021] Preferably, in step (2), 1-vinylimidazole and 1,8-dichlorooctane are added, then hydroquinone is added for heating. After cooling, it is dissolved in dichloromethane, and then added to anhydrous ether and stirred to obtain the crosslinking agent IL-8.

[0022] Preferably, in step (2), the dichloride is 1,6-dichlorohexane; when 1,6-dichlorohexane is selected, the carbon chain steric hindrance and molecular weight of the prepared IL-6 as the crosslinking agent are moderate.

[0023] Preferably, in step (2), the heating temperature is 60-100 °C and the time is 12-48 h.

[0024] Further preferably, in step (2), the heating is carried out in an oven, and the temperature control program of the oven is as follows: (a) heating process: heating to 80 °C at a heating rate of 1-10 °C / min; (b) constant temperature process: maintaining at 80 °C for 24 h.

[0025] Preferably, in step (3), the molar ratio of [VBIM][Cl] to the crosslinking agent IL is 1:0.05-0.2.

[0026] Further preferably, the molar ratio of [VBIM][Cl] to the crosslinking agent IL is 1:0.1.

[0027] Preferably, in step (3), the time of ultraviolet light irradiation is 10-120 s.

[0028] Further preferably, the time of ultraviolet light irradiation is 30 s.

[0029] Preferably, in step (3), the photoinitiator includes 2-hydroxy-2-methyl-1-phenylpropan-1-one.

[0030] Further preferably, the dosage of 2-hydroxy-2-methyl-1-phenylpropan-1-one is 3 wt%.

[0031] Preferably, in step (3), the solid content is 60 wt%.

[0032] Preferably, in step (4), the infiltration time is 30 - 60 min.

[0033] Further preferably, the infiltration time is 30 min.

[0034] Preferably, in step (4), the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate with a volume content of 50% is ultrasonically dispersed in methanol, then brushed on the PILs coating for infiltration, and then washed with water to obtain a hydrophilic artificial stone coating; or the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate with a volume content of 40% is ultrasonically dispersed in methanol, then brushed on the PILs coating for infiltration, and then washed with water to obtain a hydrophobic artificial stone coating.

[0035] The second aspect of the present invention provides an artificial stone coating.

[0036] Specifically, the artificial stone coating is prepared by the preparation method provided in the first aspect.

[0037] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0038] (1) The present invention prepares the functionalized ionic liquid [VBIM][Cl] from 1-vinylimidazole and 1-chlorobutane for the subsequent preparation of the polyionic liquid PILs coating, and enhances the cationic framework strength of the polyionic liquid PILs coating by preparing a crosslinking agent. Its anions are combined with the cationic framework through electrostatic adsorption, providing conditions for subsequent functionalization and customization;

[0039] (2) The present invention cleverly utilizes the anion exchange property of polyionic liquid to construct the PILs coating, and the hydrophilic and hydrophobic properties of the coating surface can be changed by the type, concentration and infiltration time of the ionic liquid, meeting the versatility of different scenarios through rapid adjustability;

[0040] (3) The present invention uses artificial stone as a carrier to prepare a coating with variable hydrophilic and hydrophobic properties, making the surface of the artificial stone have anti-fouling or moisture-proof effects, and the coating is non-volatile, non-flammable, green and odorless, with good chemical stability and thermal stability. Description of the Drawings

[0041] Figure 1 It is a schematic diagram of the principle of the preparation method of the artificial stone coating of the present invention. Specific embodiments

[0042] In order to make those skilled in the art more clearly understand the technical solutions described in the present invention, the following examples are listed for illustration. It should be noted that the following examples do not limit the scope of protection required by the present invention.

[0043] In the following examples, the raw materials, reagents or devices used can be obtained from conventional commercial channels or can be obtained by existing known methods without special instructions.

[0044] Example 1

[0045] A preparation method of an artificial stone coating.

[0046] It includes the following steps:

[0047] (1) First, 1-vinylimidazole and 1-chlorobutane with a molar ratio of 1.2:1 are added to a container, and then a small amount of hydroquinone is added and stirred, followed by heating in an oven. The temperature control program of the oven is as follows: (a) Heating process: The temperature is raised to 60 °C at a heating rate of 1-10 °C / min; (b) Constant temperature process: It is placed at 60 °C for 24 h. After natural cooling, it is dissolved in dichloromethane and then added dropwise to anhydrous ether with rapid stirring to remove unreacted monomer impurities, obtaining 1-vinyl-3-butylimidazole chloride, denoted as [VBIM][Cl];

[0048] (2) 1-vinylimidazole and 1,6-dichlorohexane with a molar ratio of 2.2:1 are added to a container, and then a small amount of hydroquinone is added and stirred, followed by heating in an oven. The temperature control program of the oven is as follows: (a) Heating process: The temperature is raised to 80 °C at a heating rate of 1-10 °C / min; (b) Constant temperature process: It is placed at 80 °C for 24 h. After natural cooling, it is dissolved in dichloromethane and then added dropwise to anhydrous ether with rapid stirring to remove unreacted monomer impurities, obtaining the cross-linking agent IL-6 for ionic liquid polymerization;

[0049] (3) [VBIM][Cl] is added to MeOH, stirred and ultrasonically dispersed, with a solid content of 60 wt%, the cross-linking agent IL is added, the molar ratio of [VBIM][Cl] to the cross-linking agent IL is 1:0.1, and 3 wt% of the photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone is added while stirring. Then it is loaded on an inert carrier by spraying method, and polymerization is initiated by ultraviolet light irradiation for 30 s to obtain a polyionic liquid coating material, that is, a PILs coating is prepared;

[0050] (4) Disperse ionic liquid BMIMBF4 with a volume content of 10% by ultrasonic dispersion in MeOH, then brush it on the PILs coating and soak for 30 min. A hydrophilic artificial stone coating can be obtained through anion exchange by rinsing with water.

[0051] Disperse ionic liquid BMIMPF6 with a volume content of 10% by ultrasonic dispersion in MeOH, then brush it on the PILs coating and soak for 30 min. A hydrophobic artificial stone coating can be obtained through anion exchange by rinsing with water.

[0052] Example 2

[0053] A preparation method of an artificial stone coating.

[0054] The difference from Example 1 is that in step (4) of Example 2, ionic liquid BMIMBF4 with a volume content of 20% is dispersed by ultrasonic dispersion in MeOH, then brushed on the PILs coating and soaked for 30 min. A hydrophilic artificial stone coating can be obtained through anion exchange by rinsing with water.

[0055] Disperse ionic liquid BMIMPF6 with a volume content of 20% by ultrasonic dispersion in MeOH, then brush it on the PILs coating and soak for 30 min. A hydrophobic artificial stone coating can be obtained through anion exchange by rinsing with water.

[0056] Example 3

[0057] A preparation method of an artificial stone coating.

[0058] The difference from Example 1 is that in step (4) of Example 3, ionic liquid BMIMBF4 with a volume content of 30% is dispersed by ultrasonic dispersion in MeOH, then brushed on the PILs coating and soaked for 30 min. A hydrophilic artificial stone coating can be obtained through anion exchange by rinsing with water.

[0059] Disperse ionic liquid BMIMPF6 with a volume content of 30% by ultrasonic dispersion in MeOH, then brush it on the PILs coating and soak for 30 min. A hydrophobic artificial stone coating can be obtained through anion exchange by rinsing with water.

[0060] Example 4

[0061] A preparation method of an artificial stone coating.

[0062] The difference from Example 1 is that in step (4) of Example 4, ionic liquid BMIMBF4 with a volume content of 40% is dispersed by ultrasonic dispersion in MeOH, then brushed on the PILs coating and soaked for 30 min. A hydrophilic artificial stone coating can be obtained through anion exchange by rinsing with water.

[0063] The ionic liquid BMIMPF6 with a volume content of 40% is ultrasonically dispersed by MeOH, then brushed on the PILs coating and infiltrated for 30 min, and a hydrophobic artificial stone coating can be obtained through anion exchange by rinsing with water.

[0064] Example 5

[0065] A preparation method of an artificial stone coating.

[0066] The difference from Example 1 is that in step (4) of Example 5, the ionic liquid BMIMBF4 with a volume content of 50% is ultrasonically dispersed by MeOH, then brushed on the PILs coating and infiltrated for 30 min, and a hydrophilic artificial stone coating can be obtained through anion exchange by rinsing with water;

[0067] The ionic liquid BMIMPF6 with a volume content of 50% is ultrasonically dispersed by MeOH, then brushed on the PILs coating and infiltrated for 30 min, and a hydrophobic artificial stone coating can be obtained through anion exchange by rinsing with water.

[0068] Example 6

[0069] A preparation method of an artificial stone coating.

[0070] The difference from Example 1 is that in step (4) of Example 6, the ionic liquid BMIMBF4 with a volume content of 60% is ultrasonically dispersed by MeOH, then brushed on the PILs coating and infiltrated for 30 min, and a hydrophilic artificial stone coating can be obtained through anion exchange by rinsing with water;

[0071] The ionic liquid BMIMPF6 with a volume content of 60% is ultrasonically dispersed by MeOH, then brushed on the PILs coating and infiltrated for 30 min, and a hydrophobic artificial stone coating can be obtained through anion exchange by rinsing with water.

[0072] Example 7

[0073] A preparation method of an artificial stone coating.

[0074] The difference from Example 1 is that in step (4) of Example 7, the ionic liquid BMIMBF4 with a volume content of 70% is ultrasonically dispersed by MeOH, then brushed on the PILs coating and infiltrated for 30 min, and a hydrophilic artificial stone coating can be obtained through anion exchange by rinsing with water;

[0075] The ionic liquid BMIMPF6 with a volume content of 70% is ultrasonically dispersed by MeOH, then brushed on the PILs coating and infiltrated for 30 min, and a hydrophobic artificial stone coating can be obtained through anion exchange by rinsing with water.

[0076] Comparative Example 1

[0077] A preparation method of an artificial stone coating.

[0078] Different from Example 1, in Comparative Example 1, BMIMBF4 is not added in step (4), MeOH is used to brush and soak on the PILs coating for 30 min, and a hydrophilic artificial stone coating can be obtained through anion exchange by rinsing with water;

[0079] BMIMPF6 is not added, MeOH is used to brush and soak on the PILs coating for 30 min, and a hydrophobic artificial stone coating can be obtained through anion exchange by rinsing with water.

[0080] Results:

[0081] Table 1 Hydrophilicity detection of polyionic liquid PILs coating at the same soaking time

[0082] Specific Embodiment Infiltration Time min <![CDATA[Volume content of BMIMBF4 %]]> Contact Angle ° Example 1 30 10 74 Example 2 30 20 67 Example 3 30 30 51 Example 4 30 40 46 Example 5 30 50 42 Example 6 30 60 42 Example 7 30 70 41 Comparative Example 1 30 0 87

[0083] Table 2 Hydrophobicity detection of polyionic liquid PILs coating at the same soaking time

[0084]

[0085]

[0086] As shown in Tables 1 and 2, the volume content of hydrophilic ionic liquid BMIMBF4 and hydrophobic ionic liquid hydrophobic BMIMPF6 in the solution affects the surface properties of polyionic liquid PILs coatings under constant immersion time by using the control variable method. From the effect point of view, as the volume content of BMIMBF4 solution increases, the hydrophilicity of the polyionic liquid PILs coating becomes stronger at the same immersion time, gradually changing from weak hydrophilicity to strong hydrophilicity. When the volume content of BMIMBF4 solution reaches 50% (v / v), the hydrophilicity of the polyionic liquid PILs coating no longer changes significantly, and the contact angle is 42°; as the volume content of BMIMPF6 solution increases, at the same immersion time, the hydrophobic type of the polyionic liquid PILs coating becomes stronger, gradually changing from weak hydrophilicity to hydrophobicity. When the volume content of BMIMPF6 solution reaches 40% (v / v), the hydrophobicity of the polyionic liquid PILs coating no longer changes significantly, and the contact angle is 124°. Therefore, the preparation method of the artificial stone coating of the present invention can enhance or reduce the affinity of the coating to water droplets according to different use environments, so as to achieve the anti-fouling and moisture-proof effects respectively. Based on the climate characteristics of high humidity all year round in South China, the surface coating of artificial stone can form a solid waterproof layer, effectively preventing rainwater from penetrating, avoiding moisture from damaging the wall structure, making the surface less prone to dust, air pollution and biological corrosion, etc., protecting the surface of the building from the invasion of the natural environment, improving the service life and decorative effect of the building, and facilitating cleaning and maintenance. The adjustability of its surface hydrophilic and hydrophobic properties has important practical value for improving its versatility in different humidity scenes.

[0087] In addition, the polymerized monomers in the prepared PILs coating are non-volatile, non-flammable, green and odorless, have good chemical stability and thermal stability, and the mechanical strength of the cationic skeleton network is enhanced by cross-linking agents.

[0088] The preferred specific embodiments of the present invention are described in detail above. It should be understood that a person skilled in the art can make many modifications and changes based on the concept of the present invention without creative work. Therefore, any technical solution obtained by any modification, equivalent replacement, improvement, etc. made by a person skilled in the art based on the concept of the present invention through logical analysis, reasoning or limited experiments on the basis of the prior art shall be within the scope of protection determined by the claims.

Claims

1. A preparation method of an artificial stone coating, characterized in that, It includes the following steps: (1) First, add 1-vinylimidazole and 1-chlorobutane, then add hydroquinone and heat. After cooling, dissolve it with dichloromethane, and then add it to anhydrous ether and stir to obtain [VBIM][Cl]; (2) Add 1-vinylimidazole and dichloride, then add hydroquinone and heat. After cooling, dissolve it with dichloromethane, and then add it to anhydrous ether and stir to obtain crosslinking agent IL; (3) Add [VBIM][Cl] to methanol and stir. The solid content is 40-70 wt%, add crosslinking agent IL, add 1-5 wt% photoinitiator while stirring, and then load it on an inert carrier and irradiate with ultraviolet light to obtain a PILs coating; (4) Ultrasonically disperse ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate with a volume content of 10-80% in methanol, then brush it on the PILs coating and soak it, and rinse with water to obtain a hydrophilic artificial stone coating; or ultrasonically disperse ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate with a volume content of 10-80% in methanol, then brush it on the PILs coating and soak it, and rinse with water to obtain a hydrophobic artificial stone coating; In step (2), the dichloride is any one of 1,4-dichlorobutane, 1,6-dichlorohexane, and 1,8-dichlorooctane.

2. The preparation method according to claim 1, characterized in that, In step (1), the molar ratio of 1-vinylimidazole to 1-chlorobutane is 1-1.3:

1.

3. The preparation method according to claim 1, characterized in that, In step (1), the heating temperature is 40-80 °C and the time is 12-48 h.

4. The preparation method according to claim 1, wherein In step (2), the molar ratio of 1-vinylimidazole to dichloride is 2-2.3:

1.

5. The preparation method according to claim 1, characterized in that, In step (2), the dichloride is 1,6-dichlorohexane.

6. The preparation method according to claim 1, characterized in that, In step (3), the molar ratio of [VBIM][Cl] to crosslinking agent IL is 1:0.05-0.

2.

7. The preparation method according to claim 1, characterized in that, In step (3), the ultraviolet light irradiation time is 10-120 s.

8. The preparation method according to claim 1, wherein, In step (3), the photoinitiator includes 2-hydroxy-2-methyl-1-phenyl-1-propanone.

9. The preparation method according to claim 1, wherein, In step (4), the soaking time is 30-60 min.

10. An artificial stone coating prepared by the preparation method according to any one of claims 1 to 9.

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