CN110862712A - Slow-release snow-melting agent and preparation method of snow-melting coating thereof - Google Patents
Slow-release snow-melting agent and preparation method of snow-melting coating thereof Download PDFInfo
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- C08F2438/00—Living radical polymerisation
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Abstract
The invention relates to a slow-release snow-melting agent and a preparation method of a snow-melting coating thereof. The prepared slow-release snow-melting agent is characterized in that water-soluble inorganic or organic salt is coated in amphiphilic block copolymer vesicle micelles. The amphiphilic block copolymer comprises a block copolymer of polyacrylic acid and polystyrene, a block copolymer of poly-N, N-dimethylacrylamide and polystyrene and the like. The invention selects the amphiphilic block copolymer as the coating material, the hydrophilic chain segment has better compatibility with water-soluble inorganic/organic salt, the better coating effect on the water-soluble inorganic/organic salt can be realized, the hydrophobic chain segment polystyrene has better compatibility with organic silicon coating, the construction is easier, and when the coating is used for the snow-melting coating, the snow-melting coating formed by the snow-melting coating has excellent hydrophobicity, slow release property and durable service life.
Description
Technical Field
The invention relates to a slow-release snow-melting agent and a preparation method thereof.
Background
The problem that the road traffic safety is disturbed by the ice accumulated on the road surface in winter is always. The ice accumulated on the road surface can cause the anti-skid capability of the road surface to be greatly reduced, thereby weakening the traffic capacity of the road, easily causing malignant traffic accidents, damaging the road and the accessory structures thereof, causing traffic interruption in serious cases, causing the life and production of people to be unable to be normally carried out, and even harming the safety of life and property of people.
At present, the common methods for removing ice and snow on the road surface are generally divided into two types, namely a passive inhibition type and an active ice and snow melting type. The commonly adopted passive inhibition type ice and snow removing measures mainly comprise measures of spreading a snow melting agent, manually removing snow, mechanically removing snow and the like. The main components of the metal chloride snow-melting agent which is usually scattered are sodium chloride, calcium chloride, magnesium chloride, potassium chloride and the like, which can not only ensure smooth traffic and safe driving, but also corrode infrastructure and destroy the environment. The manual snow removal and the mechanical snow removal are low in efficiency and long in time consumption, and particularly, professional snow removal equipment needs to be purchased for the mechanical snow removal, so that the road surface is damaged. Besides the defects, the methods have hysteresis, and can not remove ice in time under complex conditions such as night and the like, so that the probability of traffic accidents is greatly improved. The active ice and snow melting technology mainly realizes ice and snow melting through special functions of the road surface, and comprises a self-stress elastic road surface paving technology, an energy conversion type ice and snow melting technology and the like. The active ice and snow melting type technique is not yet mature, and the actual operation is difficult. Some studies have been made in the prior art on sustained-release snow-melting agents.
Patent 2 discloses a slow-release type three-component deicing and snow melting coating, wherein the resin used is an organic silicon material and an ice-suppressing component comprising salts and carbon black loaded on a porous adsorption carrier such as zeolite is adopted. However, although the coating has a slow release property and anti-freezing property, the composition thereof is complicated and the preparation process is cumbersome, resulting in disadvantages to the on-site construction of the road surface; in addition, the anti-freezing and sustained release properties of the ice-suppressing component still remain to be further improved.
Patent document 3 discloses an organic-coated slow-release long-acting environmentally-friendly snow-melting and ice-melting agent which can be used in a self-snow-melting coating, and the preparation method comprises heating and compounding a snow-melting salt and an organic coating agent by using a twin-screw extruder. Although the snow-melting ice-melting agent can lower the freezing point, patent document 3 does not pay attention to whether the snow-melting ice-melting agent can maintain its performance when used in an anti-icing coating. In addition, patent document 3 adopts a twin-screw extruder and has a heating and cooling process, which results in a high production cost.
In addition, wax, asphalt, or the like has been used in the prior art to coat inorganic salts to impart sustained release properties. However, the prior art has the following problems: since the inorganic salt particles are small (large specific surface area), the amount of wax, asphalt, or various resins (e.g., patent document 3) used may be large and uneconomical; by adopting the simple physical mode for wrapping, the wrapping on the surface of the particles is difficult to be uniform, the organic matter has viscosity, the wrapped particles can be bonded together, in order to disperse the bonded particles, the workload of subsequent production can be huge, and the real industrialization is difficult to realize. The invention selects the amphiphilic block copolymer as the coating material, the hydrophilic chain segment has better compatibility with water-soluble inorganic/organic salt, the better coating effect on the water-soluble inorganic/organic salt can be realized, the hydrophobic chain segment polystyrene has better compatibility with organic silicon coating, the construction is easier, and when the invention is used for snow-melting coating, the snow-melting coating formed by the snow-melting coating has excellent hydrophobicity, slow release property and durable service life
Patent document 1: CN108707452A
Patent document 2: CN103805059A
Patent document 3: CN107699199A
Disclosure of Invention
Problems to be solved by the invention
In view of the above problems, an object of the present invention is to provide a sustained-release snow-melting agent having an excellent sustained-release property and a long life.
Another object of the present invention is to provide a method for producing the sustained-release snow melt agent, which can be carried out in a simple manner.
The slow release snow-melting agent comprises a coating material and a water-soluble inorganic or organic salt, wherein the coating material is an amphiphilic block copolymer vesicular micelle, and the coated material is the water-soluble inorganic or organic salt.
The amphiphilic block copolymer is one or two of a block copolymer of acrylic acid and styrene, a block copolymer of N, N-dimethylacrylamide and styrene, a block copolymer of hydroxyethyl acrylate and styrene and a block copolymer of methacrylic acid-2- (dimethylamino) ethyl ester and styrene.
The water-soluble metal salt is at least one selected from potassium chloride, sodium acetate, potassium acetate and potassium formate.
Dispersing styrene, a macromolecular chain transfer agent solution, an initiator and water-soluble inorganic or organic salt in an ethanol/water or methanol/water mixed solution for styrene dispersion polymerization, reacting at 50-80 ℃ for 10-30h, simultaneously performing styrene polymerization and in-situ assembly to form amphiphilic polymer vesicle micelles, and coating the water-soluble inorganic or organic salt in the inner cavities of the polymer vesicles in the micelle forming process; wherein the mass ratio of the macromolecular chain transfer agent, the styrene and the initiator is 1: (100-1000): (0.1-2), the concentration of the water-soluble organic salt or inorganic salt is 0.1-3 mol/L;
the macromolecular chain transfer agent is selected from one or two of polyacrylic acid, poly N, N-dimethylacrylamide, polyhydroxyethyl acrylate and poly 2- (dimethylamino) ethyl methacrylate.
The preparation method of the macromolecular chain transfer agent comprises the following steps:
one or two of water-soluble monomer acrylic acid, N-dimethylacrylamide, hydroxyethyl acrylate and N, N-dimethylacrylamide, one of chain transfer agents S-1-dodecyl-S '(α - α' -dimethyl- α 'acetic acid) -trithiocarbonate, S' -bis (α '-methyl- α' -acetic acid) trithiocarbonate and dibenzyl trithiocarbonate, and an initiator are dissolved in methanol/ethanol and react for 2-10 hours at 50-70 ℃ to prepare a methanol or ethanol solution of the macromolecular chain transfer agent, wherein the mass ratio of the water-soluble monomer, the chain transfer agent and the initiator is (20-100): 1 (0.1-2).
A slow release snow melting coating comprising: 10-70 parts by mass of asphalt, 0.5-5.0 parts by mass of curing catalyst, 5-40 parts by mass of filler, 0.5-40 parts by mass of silane coupling agent and 10-55 parts by mass of sustained-release snow melting modifier according to any one of [1] to [2] relative to 100 parts by mass of organosilicon material.
The curing catalyst includes, but is not limited to, organic titanium compounds: titanium tetraisopropoxide, titanium tetra-t-butoxide, titanium di (isopropoxide) bis (ethylacetoacetate), titanium di (isopropoxide) bis (acetoacetoacetate)); organotin compound: dibutyltin dilaurate, dibutyltin diacetylacetoacetate, and tin octoate; metal dicarboxylate: lead dioctoate; an organozirconium compound: zirconium tetraacetylacetonate; an organoaluminum compound: aluminum triacetylacetonate; amine: hydroxylamine and tributylamine.
The organic silicon material is at least one selected from organic silicon resin, organic silicon modified polyurethane resin, organic silicon modified epoxy resin, organic silicon modified acrylate resin, fluorine modified organic silicon resin, organic silicon modified polyester resin, organic silicon modified phenolic resin, organic silicon modified styrene-acrylic rubber and organic silicon modified styrene-butadiene rubber.
The filler is one or more of carborundum, silicon dioxide, carbon black, clay, mica, talc and hard resin particles.
The slow-release snow-melting coating also comprises a silane coupling agent.
Description of the drawings:
FIG. 1 is a Transmission Electron Microscope (TEM) image of micelle of polyacrylic acid-polystyrene block copolymer vesicles in production example 1.
FIG. 2 is a Transmission Electron Microscope (TEM) image of poly-N, N-dimethylacrylamide-polystyrene-poly-N, N-dimethylacrylamide block copolymer vesicle micelles in production example 2.
FIG. 3 is a Transmission Electron Microscope (TEM) image of polyacrylic acid-polystyrene block copolymer vesicles coated with potassium chloride in production example 3.
FIG. 4 is a Transmission Electron Microscope (TEM) image of poly (N, N-dimethylacrylamide-polystyrene) block copolymer coated with sodium acetate in production example 4.
FIG. 5 is Transmission Electron Micrographs (TEM) of poly (N, N-dimethylacrylamide-polystyrene) block copolymer coated with potassium formate of production example 5, respectively.
Fig. 6ab is a water droplet state when water droplets are dropped onto an uncoated glass slide and a glass slide having a coating layer formed of the sustained-release snow-melting agent coating material of production example 3, respectively.
Fig. 7ab shows the case when water droplets were dropped on an uncoated general road surface and a road surface having a coating layer formed of the sustained-release snow-melting agent coating material of production example 3, respectively.
Fig. 8ab shows the deicing effects of the coating formed from the reference paint and the coating formed from the anti-ice-freezing paint of production example 3, respectively.
Detailed Description
The other components except the sustained-release snow-melting modifier in the sustained-release snow-melting paint constituting the present invention will be described in detail below.
< snow melting coating >
The snow-melting coating of the present invention can form a snow-melting coating layer after being applied to an asphalt pavement and cured. Specifically, the snow-melting coating comprises, relative to 100 parts by mass of an organosilicon material, 10-70 parts by mass of asphalt, 0.5-5.0 parts by mass of a curing catalyst, 5-40 parts by mass of a filler, 0.5-40 parts by mass of a silane coupling agent, and 10-55 parts by mass of a slow-release snow-melting modifier. The amount of "relative to 100 parts by mass of the silicone material" used herein means the content of the solid content of each component relative to the solid content of the silicone material.
In the snow-melting coating, the physical and chemical actions (affinity) between the snow-melting modifier and other components are good, so that the snow-melting modifier is not easy to damage in use and can keep the snow-melting property and slow release property for a long time; in addition, the organosilicon material and the asphalt are present in a specific ratio, so that the coating obtained after the coating is cured shows excellent hydrophobicity, strong bonding force with a road surface and impact resistance to external force, thereby improving the service life of the coating.
It is to be noted that the content of the snow melt modifier of the present invention is preferably 15 to 45 parts by mass, more preferably 20 to 40 parts by mass, relative to 100 parts by mass of the silicone-based material. When the content of the snow melt modifier is more than the above range, the amount of the snow melt ingredient (water-soluble metal salt) released during use tends to be excessively large, resulting in adverse effects on the environment. When the content of the snow melt modifier is less than the above range, the snow melt property tends to deteriorate. The compositions other than the snow melt modifier described above in the snow melt coating material constituting the present invention will be described in detail below.
< Silicone-based Material >
In the invention, when the organic silicon material is used for the snow melting coating, the cured snow melting coating and the asphalt pavement have strong binding force, and simultaneously, good hydrophobicity and affinity with the slow-release snow melting modifier are provided, so that the service life and the snow melting property are improved.
The organosilicon material is a polymer with a repeating unit of silicon-oxygen bond (-Si-O-) in the molecule, and can be crosslinked and cured in the presence of a curing catalyst. Preferably, the organic silicon material is at least one selected from organic silicon resin, organic silicon modified polyurethane resin, organic silicon modified epoxy resin, organic silicon modified acrylate resin, fluorine modified organic silicon resin, organic silicon modified polyester resin, organic silicon modified phenolic resin, organic silicon modified styrene-acrylic rubber and organic silicon modified styrene-butadiene rubber.
It should be noted that the term "silicone-modified acrylate-based resin" in the present invention means a general term of "silicone-modified methacrylate-based resin" and "silicone-modified acrylate-based resin".
The form of the silicone-based material is not particularly limited. In the present invention, the silicone material is preferably added in the form of a silicone emulsion from the viewpoint of processability. In this case, the solid content of the silicone emulsion is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and still more preferably 30 to 60% by mass.
The silicone-based material used in the present invention may be a commercially available product, for example, produced by Wacker chemistry
EL 39、
FF 230VP、
PN 100、
CONCENTRATE、
NF S、
AE 54、
AE 61、
AE 66、
PE 280、
BS 1360、
BS 16040, etc.; MEM-0075, DC 349, IE-6683, MEM-8194, Xiaometer MEM-3422, Xiaometer MEM-8031, etc., manufactured by Dow Corning; WA-1, WS-3, ND7509, etc. made by Shandong Wuhu lake chemical industry.
< asphalt >
In the present invention, when asphalt is used in the slow-release type snow-melting coating material, there is excellent affinity between the slow-release type snow-melting coating layer and the asphalt pavement after coating is kept in a dark tone. In addition, the impact resistance of the snow-melting coating is improved due to the plasticity of the asphalt.
The kind of asphalt used in the slow-release snow-melting coating material of the present invention is not particularly limited, and may be coal tar asphalt, petroleum asphalt, natural asphalt, and various modified products thereof. Examples of the modified product include resin-modified asphalt such as epoxy-modified asphalt and urethane-modified asphalt, and rubber-modified asphalt such as styrene-butadiene rubber-modified asphalt.
From the viewpoint of improving both the impact resistance and the hydrophobicity of the snow-melt coating layer, the content of the asphalt is 10 to 70 parts by mass, preferably 15 to 60 parts by mass, and more preferably 20 to 50 parts by mass, relative to 100 parts by mass of the silicone-based material. When the content of asphalt is less than the above range, the cost tends to be excessively large, the impact resistance of the snow-melt coating tends to deteriorate, and the color of the snow-melt coating tends to be excessively light to cause a reduction in the safety of asphalt pavement. When the content of the asphalt is more than the above range, the hydrophobicity and wear resistance of the snow-melt coating layer tend to deteriorate. In addition, the service life of the snow melt coating tends to be reduced whether the content of the asphalt is too large or too small.
The form of the asphalt is not particularly limited, and may be diluted asphalt, emulsified asphalt, or the like. From the viewpoint of workability, emulsified asphalt is preferably used. In the case of using the emulsified asphalt, the solid content of the emulsified asphalt is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and still more preferably 40 to 60% by mass.
The properties of the emulsified asphalt usable in the present invention preferably satisfy the indexes shown in the following table 1.
TABLE 1
Note: the detection method is carried out according to a method specified in the industry Standard road engineering asphalt and asphalt mixture test Specification IJG E20.
< curing catalyst >
In the present invention, the curing catalyst is used to crosslink and cure the snow-melting coating. The curing catalyst of the present invention is not particularly limited, and examples thereof include, but are not limited to, organic titanium compounds such as titanium tetraisopropoxide, titanium tetra-t-butoxide, titanium di (isopropoxide) bis (ethylacetoacetate), titanium di (isopropoxide) bis (acetoacetato) titanium; organotin compounds such as dibutyltin dilaurate, dibutyltin bisacetoacetate, and tin octylate; metal dicarboxylates such as lead dioctoate; organozirconium compounds such as zirconium tetraacetylacetonate; organoaluminum compounds such as aluminum triacetylacetonate; and amines such as hydroxylamine and tributylamine.
The content of the curing catalyst is 0.5 to 5.0 parts by mass, preferably 0.8 to 4.5 parts by mass, and more preferably 1.0 to 4.0 parts by mass, based on 100 parts by mass of the silicone material. If the content of the curing catalyst is too small, the curing property of the coating material of the present invention tends to be insufficient, and the excessive use tends to result in a loss of storage stability.
< Filler and silane coupling agent >
The snow-melting coating also comprises a filler, so that the strength and the skid resistance of the snow-melting coating are further improved. Examples of fillers of the present invention include, without limitation, silicon carbide, silica, carbon black, clay, mica, talc, hard resin particles, and the like. They may be used alone or in a combination of two or more. The content of the filler is preferably 5 to 40 parts by mass, more preferably 10 to 30 parts by mass, relative to 100 parts by mass of the silicone material.
The size of the filler is preferably 10 to 60 mesh, more preferably 20 to 50 mesh, and still more preferably 24 to 45 mesh.
The silane coupling agents of the present invention are known in the art, and examples thereof include, but are not limited to, vinyltris (β -methoxyethoxy) silane, gamma-methacryloxypropyltrimethoxysilane (KH-570), gamma-methacryloxypropyltriethoxysilane, gamma-methacryloxypropyltripropoxysilane, gamma-methacryloxyethyltrimethoxysilane, gamma-methacryloxyethyltriethoxysilane, gamma-methacryloxyethyltripropoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, N- β - (aminoethyl) gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane (KH-550), gamma-aminopropyltripropoxysilane, gamma-mercaptopropyltrimethoxysilane (KH-590), gamma-mercaptopropyltriethoxysilane, gamma-2- (dimethoxypropyl) triethoxysilane, gamma-3- (2, 2- (2-glycidoxypropyl) trimethoxysilane (3, 2- (2-glycidoxypropyl) trimethoxysilane, 2- (2-glycidoxypropyl) trimethoxysilane, 2- (3, 2-glycidoxypropyl) trimethoxysilane, 2- (2-glycidoxypropyl) trimethoxysilane, 2-glycidoxypropyl) trimethoxysilane, 2- (glycidoxy) trimethoxysilane, 2,3, 2-glycidoxy) ethyl-glycidoxy silane, and the like.
In order to more effectively exert the function of the silane coupling agent, the mass ratio of the silane coupling agent to the filler (silane coupling agent/filler) is preferably 1/15 to 2/1, more preferably 1/10 to 1/1, and still more preferably 1/8 to 1/2.
< other additives >
The snow-melting paint of the present invention may further contain 1 or 2 or more kinds of other additives such as a thermal crosslinking agent, a polymer dispersant, a dispersion aid, a curing accelerator, a thickener, a plasticizer, a defoaming agent, a leveling agent, an anti-shrinking agent, and an ultraviolet absorber, as required.
< preparation method of snow-melting coating >
The snow-melting coating of the present invention can be obtained by mixing a silicone-based material, asphalt, a silane coupling agent, a catalyst, the slow-release snow-melting modifier of the present invention, and, as required, a filler, a silane coupling agent, and the other components described above. The order of addition of the components constituting the anti-icing coating is not particularly limited, and the above-mentioned mixing can be carried out using a conventionally known mixer.
< curing of snow-melting coating >
The curing temperature of the snow-melting coating material of the present invention is not particularly limited. Preferably, the curing of the snow melt coating of the present invention is typically carried out at ambient temperature for outdoor construction needs.
The present invention is further illustrated by the following examples, but the present invention is not limited to the following examples. Unless otherwise specified, the term "parts" means "parts by mass", and "%" means "% by mass".
Production example 1:
Step 2: adding 8g of styrene, 5g of the product obtained in the step 1, 0.03g of azobisisobutyronitrile, 15g of ethanol and 5g of water into a bottle with a branch mouth, introducing argon, bubbling for 10 minutes, pumping for 7 times, removing oxygen in the system, placing the system in a constant-temperature oil bath kettle at 70 ℃, and reacting for 8 hours to stop the reaction.
Production example 2:
Step 2: adding 8g of styrene, 5g of the product obtained in the step 1, 0.04g of azobisisoheptonitrile, 20g of methanol and 3g of water into a bottle with a branch mouth, introducing argon, bubbling for 10 minutes, pumping for 7 times, removing oxygen in the system, placing the system in a constant-temperature oil bath kettle at 70 ℃, and reacting for 6 hours to stop the reaction.
Production example 3:
Step 2: adding 8g of styrene, 5g of the product obtained in the step 1, 0.03g of azobisisobutyronitrile and 15g of ethanol into a bottle with a branch mouth, dissolving 0.6g of potassium chloride into 5g of water, dropwise adding a potassium chloride solution into the bottle with the branch mouth, introducing argon for bubbling for 10 minutes, pumping and discharging for 7 times, removing oxygen in the system, placing the system in a constant-temperature oil bath kettle at 70 ℃, and reacting for 8 hours to stop the reaction.
Production example 4:
Step 2: 8g of styrene, 5g of the product obtained in the step 1, 0.04g of azobisisoheptonitrile and 20g of methanol, 1g of sodium acetate is dissolved in 3g of water, the sodium acetate solution is dripped into a branched bottle, argon is introduced for bubbling for 10 minutes, the reaction is pumped and discharged for 7 times, oxygen in the system is removed, the mixture is placed in a constant-temperature oil bath kettle at 70 ℃, and the reaction is stopped after 6 hours of reaction.
Production example 5:
a sustained-release snow-melting agent was obtained in the same manner as in production example 4, except that sodium acetate was changed to potassium formate in production example 4.
Comparative production example 1
4g of industrial potassium chloride and 5g of silane coupling agent KH-550 are mixed at 70 ℃ to obtain the snow-melting agent coated by the silane coupling agent.
Comparative production example 2
Adding 4g of industrial potassium chloride into water, heating (70 ℃) and stirring, adding 2g of zeolite after dissolving, fully mixing and evaporating all water to obtain the zeolite-loaded snow melting modifier.
Various slow-release snow-melting agent coatings and coatings formed therefrom were prepared in the following examples.
Example 1
Adding 40 parts of emulsified asphalt to 100 parts of Watt-Keg made by Chemicals
EL 39 organosilicon emulsion is stirred for 10min at the rotation speed of 200rpm, 16 parts of the slow-release snow melting modifier prepared in production example 3 is added and stirred for 15min at the rotation speed of 200rpm, 3 parts of vinyl tri (β -methoxyethoxy) silane is added, 1.0 part of dibutyltin dilaurate is added and stirred for 20min at the rotation speed of 300rpm, finally 10 parts of 40-mesh carborundum is added and stirred for 30min at the rotation speed of 300rpm, and the hydrophobic slow-release organosilicon coating is obtained.
Example 2
A silicone coating was obtained in the same manner as in example 1, except that the slow-release snow-melting agent modifier in example 1 was replaced with the slow-release snow-melting agent prepared in production example 4.
Example 3
A silicone coating was obtained in the same manner as in example 1, except that the slow release type snow melt modifier in example 1 was replaced with the slow release type snow melt modifier prepared in production example 5.
Comparative example 1
A silicone coating was obtained in the same manner as in example 1, except that the slow-release snow melt modifier in example 1 was replaced with a water-soluble metal salt that was not coated.
Comparative example 2
A silicone coating was obtained in the same manner as in example 1, except that the slow-release snow melt modifier in example 1 was replaced with the snow melt modifier prepared in comparative production example 1.
Comparative example 3
A silicone coating was obtained in the same manner as in example 1, except that the slow-release snow melt modifier in example 1 was replaced with the snow melt modification prepared in comparative production example 2.
Example 4
A silicone coating was obtained in the same manner as in example 1, except that the amount of the slow release snow melt modifier in example 1 was changed to 9 parts.
Comparative example 4
A silicone coating was obtained in the same manner as in example 1, except that the amount of the slow release snow melt modifier in example 1 was changed to 4 parts.
Comparative example 5
A silicone coating was obtained in the same manner as in example 1, except that the amount of the slow release snow melt modifier in example 1 was changed to 60 parts.
Example 5
A silicone coating was obtained in the same manner as in example 1, except that the amount of emulsified asphalt having a solid content of 50% in example 1 was changed to 20 parts.
Comparative example 6
A silicone coating was obtained in the same manner as in example 1, except that the amount of emulsified asphalt having a solid content of 50% in example 1 was changed to 80 parts.
Comparative example 7
A silicone coating was obtained in the same manner as in example 1, except that the amount of emulsified asphalt having a solid content of 50% in example 1 was changed to 8 parts.
Fig. 1 and 2 are transmission electron micrographs of production example 1 and production example 2, respectively, of the present invention, and polyacrylic acid-polystyrene porous spherical micelles and poly N, N-dimethylacrylamide-polystyrene-poly N, N-dimethylacrylamide vesicle micelles were obtained in the absence of water-soluble inorganic or organic salts, respectively.
FIG. 3 is a transmission electron micrograph of production example 3 of the present invention, from which it can be seen that water-soluble inorganic salt potassium chloride particles are coated in the inner cavity of polyacrylic acid-polystyrene vesicle micelle.
FIGS. 4 and 5 are transmission electron micrographs of production example 4 and production example 5, respectively, from which sodium acetate and potassium formate particles could not be directly seen, mainly due to the fact that the organic acid salt was attached to the polymer cell walls in coordination with the tertiary amino groups on the N, N-dimethylacrylamide units. Compared with the common simple physical coating, the water-soluble organic salt has slower precipitation rate and obviously improved slow release performance.
Performance testing
Hydrophobicity of the coating
The hydrophobicity of the snow-melting coat layer formed of the slow-release snow-melting coating materials in the examples and comparative examples was evaluated by the magnitude of the contact angle θ. The contact angle θ is measured with the aid of a contact angle measuring instrument. Specifically, a snow-melting coating is sprayed onto the surface of a glass slide and cured to form a snow-melting coating, and thereafter, water droplets are dropped onto the surfaces of an uncoated glass slide and a glass slide having a slow-release type snow-melting coating, respectively, and photographs are taken in comparison with the case of a static contact angle. Specific results regarding the contact angle of the slow-release snow-melting coating materials in the respective examples and comparative examples are shown in table 2.
The test results for the coating of example 1 are shown in fig. 6. The contact angle of a droplet on a glass slide with a coating formed from the coating of example 1 was 95.6 deg., while the contact angle of a droplet on a clean glass slide was 30 deg.. From the data comparison, it can be seen that the coating of the present invention has good hydrophobic properties.
Fig. 7 shows the case when water droplets are dropped on an uncoated general road surface and a road surface having a coating layer formed of the slow release type snowmelt coating material of example 1, respectively. As can be seen from FIG. 7, the anti-icing coating of the present invention significantly improves the hydrophobic anti-icing performance of the pavement.
Anti-icing properties of the coating
In the test of anti-freezing property, the test was carried out according to the following procedure. Note that a reference coating containing no snow melt modifier was also prepared in an approximate manner.
Step 1: and preparing a wet wheel abrasion test piece, sealing the edge of the wet wheel abrasion test piece by using plasticine to prevent water loss, and then coating the slow-release snow-melting coating and the reference coating on the surface of the test piece. The coating amount of the coating is based on the principle that the coating is easy to uniformly and completely cover the surface of a test piece, and the spraying amount during actual construction is taken into consideration. The coating amount of the paint on the surface of the test piece is 0.4kg/m2. The brushing amount is 0.4-0.6kg/m2May be used.
Step 2: after the coating is solidified, the rainfall and snowfall process in winter is simulated, and a certain amount of water (the amount of water is equivalent to the rainfall and snowfall amount in one area about once) is added on the surface of the test piece. It was then placed in a-15 ℃ cryostat to simulate winter climatic conditions.
And step 3: after 3 hours, the test piece is taken out, the impact effect of an automobile tire on the road surface is simulated, the test piece is dropped and impacted for 1 time from a position of 50cm by using a manual compaction instrument (with the mass of 4.5Kg), and then the cracking condition of the ice layer and the combination condition of the ice blocks and the surface of the test piece are observed.
The anti-freezing principle of the slow-release snow-melting coating is that the ice layer is broken under the action of the load of the vehicle, so that the deicing effect is achieved. Therefore, the anti-freezing performance was evaluated by visually observing the surface condition of each test piece based on whether the ice layer was easily cracked and broken after knocking the ice layer and the degree of falling off from the test piece.
Fig. 8 shows the deicing effect of the coating layer formed of the reference paint and the coating layer formed of the snow-melting paint of example 1. As shown in fig. 8, the surface of the test piece on which the coating of the reference paint was formed was very firmly adhered to the ice layer, and the ice layer was dense and could not be removed even after knocking. With this as a reference, evaluation was performed based on the following criteria.
○ the ice layer is loose and broken after knocking and falls off completely,
△ when the ice layer is knocked, the ice layer cracks more and most of the ice layer falls off,
x: after knocking, the ice layer is less cracked and difficult to fall off.
Sustained release of coating
The test of sustained-release property is specifically as follows.
Step 1: similar to step 1 in the test of anti-icing property, the sustained-release snow-melting paints prepared in examples and comparative examples were painted on the test piece.
Step 2: after the coating is dried, the rainfall and snowfall process in winter is simulated, and a certain amount of water is added on the surface of the test piece. The water was then placed at-15 ℃ with the test pieces.
And step 3: and taking out the test piece after 3 hours, simulating the impact effect of an automobile tire on the road surface, knocking the ice layer, and observing the cracking condition of the ice layer and the combination condition of the ice blocks and the surface of the test piece.
And 4, if the ice layer is fragile (reaches a level of more than △ in the anti-icing test), indicating that the coating has the anti-icing effect, removing the ice layer on the surface of the test piece, and repeating the steps 1-3.
Evaluation was performed based on the following criteria according to the number of times the test could be repeated.
○, the process can be repeated for more than 10 times,
△ can be repeated less than 10 times and more than 5 times,
x: it can be repeated for 5 times or less.
It is noted that, as technical indexes in the field, in order to meet the requirement of one winter, 5-6 times of cycle tests can be realized, and if the slow release test can be carried out more than 10 times, the technical effect is obviously superior to the conventional technical indexes at present.
The tests described above were performed on the anti-freezing modifiers obtained in the examples and comparative examples, and the evaluation results are shown in table 2.
TABLE 2
Claims (8)
1. The slow-release snow-melting agent is characterized by comprising a coating material and water-soluble inorganic or organic salt, wherein the coating material is an amphiphilic block copolymer vesicle micelle, and the coated material is water-soluble inorganic or organic salt;
the amphiphilic block copolymer is one or two of a block copolymer of acrylic acid and styrene, a block copolymer of N, N-dimethylacrylamide and styrene, a block copolymer of hydroxyethyl acrylate and styrene and a block copolymer of 2- (dimethylamino) ethyl methacrylate and styrene.
2. The sustained-release snow-melting agent according to claim 1, wherein the water-soluble metal salt is at least one selected from the group consisting of potassium chloride, sodium acetate, potassium acetate, and potassium formate.
3. A method for producing the sustained-release snow-melting agent according to any one of claims 1 or 2, comprising:
dispersing styrene, a macromolecular chain transfer agent solution, an initiator and water-soluble inorganic or organic salt in an ethanol/water or methanol/water mixed solution for styrene dispersion polymerization, reacting at 50-80 ℃ for 10-30h, simultaneously performing styrene polymerization and in-situ assembly to form amphiphilic polymer vesicle micelles, and coating the water-soluble inorganic or organic salt in the inner cavities of the polymer vesicles in the micelle forming process; wherein the mass ratio of the macromolecular chain transfer agent, the styrene and the initiator is 1: (100-1000): (0.1-2), the concentration of the water-soluble organic salt or inorganic salt is 0.1-3 mol/L;
the macromolecular chain transfer agent is selected from one or two of polyacrylic acid, poly N, N-dimethylacrylamide, polyhydroxyethyl acrylate and poly 2- (dimethylamino) ethyl methacrylate.
4. The method of claim 3, wherein the macromolecular chain transfer agent is prepared by a method comprising:
one or two of water-soluble monomer acrylic acid, N-dimethylacrylamide, hydroxyethyl acrylate and N, N-dimethylacrylamide, one of chain transfer agents S-1-dodecyl-S '(α - α' -dimethyl- α 'acetic acid) -trithiocarbonate, S' -bis (α '-methyl- α' -acetic acid) trithiocarbonate and dibenzyl trithiocarbonate, and an initiator are dissolved in methanol/ethanol and react for 2-10 hours at 50-70 ℃ to prepare a methanol or ethanol solution of the macromolecular chain transfer agent, wherein the mass ratio of the water-soluble monomer, the chain transfer agent and the initiator is (20-100): 1 (0.1-2).
5. A slow release snow melting coating comprising: 10-70 parts by mass of asphalt, 0.5-5.0 parts by mass of curing catalyst, 5-40 parts by mass of filler, 0.5-40 parts by mass of silane coupling agent and 10-55 parts by mass of slow-release snow melting modifier relative to 100 parts by mass of organic silicon material.
6. The slow release snow melt coating of claim 5 wherein the curing catalyst is one or more of the following: titanium tetraisopropoxide, titanium tetra-t-butoxide, titanium di (isopropoxide) bis (ethylacetoacetate), titanium di (isopropoxide) bis (acetoacetoacetate)); dibutyltin dilaurate, dibutyltin diacetylacetoacetate, and tin octoate; metal dicarboxylate: lead dioctoate; zirconium tetraacetylacetonate; aluminum triacetylacetonate; hydroxylamine, tributylamine.
7. The slow-release snow-melting coating according to claim 5, wherein the silicone material is at least one selected from silicone resin, silicone-modified polyurethane resin, silicone-modified epoxy resin, silicone-modified acrylate resin, fluorine-modified silicone resin, silicone-modified polyester resin, silicone-modified phenolic resin, silicone-modified styrene-acrylic rubber, and silicone-modified styrene-butadiene rubber.
8. A snow-melting coating material of the slow release type as claimed in claim 5, wherein the filler is one or more of silicon carbide, silica, carbon black, clay, mica, talc, hard resin particles.
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