CN109928655B - Core-shell type anti-icing modifier, manufacturing method thereof and anti-icing coating comprising same - Google Patents
Core-shell type anti-icing modifier, manufacturing method thereof and anti-icing coating comprising same Download PDFInfo
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Abstract
The invention relates to a core-shell type anti-freezing ice modifier, a manufacturing method thereof and an anti-freezing ice coating comprising the same. The core-shell type anticoagulation ice modifier comprises a core and a shell, wherein the core is water-soluble metal salt particles, the shell is formed by oxide particles and coats the core, and the thickness of the shell is more than 10 nm. The core-shell type anti-freezing modifier is easy to construct, and when the core-shell type anti-freezing modifier is used for an anti-freezing coating, an anti-freezing coating formed by the anti-freezing coating has excellent anti-freezing property, hydrophobicity, slow release property and long service life.
Description
Technical Field
The invention relates to a core-shell type anti-freezing ice modifier, a manufacturing method thereof and an anti-freezing ice coating comprising the same.
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. 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.
After a long period of time of research and application, it is considered that a technology of obtaining an anti-icing coating on a pavement by coating an asphalt pavement with an anti-icing coating is a more reasonable technology in consideration of cost, maintenance, action time, and use effect.
The anti-icing coating is a new-generation functional pavement coating obtained by compounding an organic hydrophobic material and an anti-icing modifier. The technology overcomes the defect that the prior maintenance technology is difficult to construct in the low-temperature environment in winter. The organic hydrophobic material has excellent adhesion with the road surface, and has air-permeable water-sealing property and self-cleaning property, so that dust covered on the surface can be automatically removed, the inhibition effect of the anti-icing modifier on the freezing point is recovered, and the deicing function is actively maintained. The main principle of the anti-freezing modifier contained in the anti-freezing coating is that components with the freezing inhibition effect inside are gradually separated out under the actions of capillary pressure and vehicle rolling, so that the freezing point of water on the surface of a road is reduced, and snow freezing on the surface of the road is inhibited. Therefore, the anti-freezing modifier used in the anti-freezing coating material is required to have excellent sustained release property due to the use cost and the need for environmental protection. Some studies have been made in the prior art on anti-ice coatings and anti-ice modifiers.
Patent document 2 discloses a super-hydrophobic anti-icing coating having a slow release function, which includes a fluoropolymer and inorganic hollow or porous nanoparticles adsorbing a small-molecule anti-icing substance. The coating has excellent hydrophobicity and slow release property, but the cost of the fluorine-containing polymer is high and the anti-freezing property and the slow release property of the inorganic hollow or porous nano particles adsorbing small molecular anti-freezing substances are insufficient.
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 present inventors have studied and found that when the anti-freezing modifier is used in an anti-freezing coating material, the anti-freezing modifier requires the use of inorganic salt particles (having a particle size of about 5 to 20 μm) in a powdery form because the thickness of the anti-freezing coating layer formed is 1mm or less. Thus, 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 particle surface 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 subsequent production workload can be very huge, and the real industrialization is difficult to realize; further, in practical use, the polymer is adopted to wrap the inorganic salt particles, so that the gaps of the wrapping material on the surfaces of the wrapped inorganic salt particles are more, and the slow-release effect is greatly reduced after the polymer is in contact with water.
Documents of the prior art
Patent document 1: CN103805059A
Patent document 2: CN102382536A
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 core-shell type anti-icing modifier which is easy to apply and, when used in an anti-icing coating, provides an anti-icing coating formed from such an anti-icing coating with excellent anti-icing properties, hydrophobicity, sustained release properties, and a long service life.
It is another object of the present invention to provide a method for producing the above-mentioned anti-icing agent, which can be carried out in a simple manner.
It is still another object of the present invention to provide an anti-icing coating comprising the aforementioned anti-icing agent, and an anti-icing coating formed from such an anti-icing coating can have excellent anti-icing properties, hydrophobicity, sustained release property, and long life.
Means for solving the problems
The present invention has been made through intensive studies by the inventors of the present invention, and is specifically as follows.
[1] A core-shell type anticoagulation modifier, which comprises a core and a shell layer, wherein the core is a water-soluble metal salt particle, the shell layer is formed by an oxide particle, and the shell layer covers the core; the thickness of the shell layer is more than 10 nm.
[2] The core-shell type anti-icing modifier according to [1], wherein the oxide particles are silica particles or titanium dioxide particles.
[3] The core-shell type anti-icing modifier according to [1] or [2], wherein the water-soluble metal salt is at least one selected from the group consisting of sodium chloride, calcium chloride, magnesium chloride, calcium acetate, magnesium acetate and potassium acetate.
[4] A method for producing the core-shell type anti-icing modifier according to any one of [1] to [3], comprising:
uniformly dispersing water-soluble metal salt in an alcohol solvent serving as an initial dispersion medium, adding an alkaline catalyst into the alcohol solvent, and optionally adding deionized water to obtain a pre-dispersion liquid;
adding a precursor of oxide particles into the pre-dispersion liquid under stirring and reacting;
the solid component was obtained by filtration, washed and dried.
[5] The process according to [4], wherein the basic catalyst is at least one selected from the group consisting of ammonia water, sodium hydroxide and potassium hydroxide.
[6] An anti-icing coating comprising: 10-70 parts by mass of asphalt, 0.5-5.0 parts by mass of curing catalyst and 10-55 parts by mass of the core-shell type anti-icing modifier according to any one of [1] to [3] relative to 100 parts by mass of the organosilicon material.
[7] The anti-ice-freezing coating according to [6], wherein 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.
[8] The anti-ice-freezing coating material according to [6] or [7], further comprising a filler.
[9] The anti-ice-freezing coating according to [8], further comprising a silane coupling agent.
ADVANTAGEOUS EFFECTS OF INVENTION
The core-shell type anti-freezing modifier is easy to construct. The core-shell type anti-icing modifier is friendly to the surrounding environment, and when the core-shell type anti-icing modifier is used for an anti-icing coating, an anti-icing coating formed by the anti-icing coating can have excellent anti-icing property at the low temperature of 0-minus 30 ℃; the core-shell type anti-icing modifier has a shell layer formed by oxide particles, so that the core-shell type anti-icing modifier has excellent hydrophobicity, and can greatly slow down the speed of releasing water-soluble metal salt, namely has excellent slow release property.
The raw materials in the preparation method are wide in source and low in price, and meanwhile, auxiliaries such as a coupling agent and a surfactant are not required to be added in the process, so that the reaction condition is mild, and the experimental period is short.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) picture of industrial NaCl used in the production example.
FIG. 2 shows NaCl/SiO solid in production example 12Scanning Electron Microscope (SEM) images of core-shell composite particles.
FIG. 3 shows NaCl/SiO in production example 22Scanning Electron Microscope (SEM) images of core-shell composite particles.
Fig. 4 shows a state of water droplets when the water droplets were dropped onto an uncoated glass slide and a glass slide having a coating layer formed of the anti-ice-freezing paint of example 1, respectively.
Fig. 5 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 anti-ice-freezing paint of example 1, respectively.
Fig. 6 shows the deicing effect of the coating layer formed of the reference paint and the coating layer formed of the anti-ice-freezing paint of example 1.
Detailed Description
< core-shell type anti-icing modifier >
The core-shell type anticoagulation ice modifier comprises a core and a shell, wherein the core is water-soluble metal salt particles, the shell is formed by oxide particles, and the core is coated by the shell. The thickness of the shell layer is more than 10 nm.
The core and shell layers constituting the core-shell type anti-icing modifier of the present invention will be described in detail below.
< core >
The core of the core-shell type anti-icing modifier is water-soluble metal salt particles. The water-soluble metal salt particles are effective components of the core-shell type anti-freezing modifier of the invention, and are used for adjusting the freezing point of water on the road surface to provide excellent anti-freezing property.
The kind of the water-soluble metal salt particles of the present invention is not particularly limited, and may be any metal salt known in the art for adjusting the freezing point of water on a road surface. From the viewpoint of better providing anti-icing property and easier availability, the water-soluble metal salt particles of the present invention are in the form of at least one kind selected from the group consisting of alkali metal chlorides, alkali metal formates, alkali metal acetates, alkaline earth metal chlorides, alkaline earth metal formates, and alkaline earth metal acetates. More preferably, the water-soluble metal salt of the present invention is preferably at least one selected from the group consisting of sodium chloride, calcium chloride, magnesium chloride, calcium acetate, magnesium acetate, and potassium acetate.
The ratio of each metal salt constituting the water-soluble metal salt particles of the present invention is not limited, and may be appropriately selected in accordance with the use temperature of the core-shell type anticoagulation ice modifier of the present invention. For example, when the core-shell type anti-freezing ice modifier is used at a temperature of 0 to-10 ℃, the mass ratio of sodium chloride to calcium chloride (magnesium chloride) may be 50-90:50-10, preferably 55-85:45-15, more preferably 60-80: 40-20; when the using temperature of the core-shell type anticoagulation ice modifier is lower than-10 ℃, the mass ratio of sodium chloride to calcium chloride (magnesium chloride) is 10-40:90-60, preferably 15-35:85-55, and more preferably 20-30: 80-70.
The shape of the water-soluble metal salt particles of the present invention is not particularly limited, and the water-soluble metal salt particles of the present invention are commercially available industrial-grade metal salts. In order to be better usable in anti-icing coatings, the water-soluble metal particles of the invention preferably have a size of 5 to 20 μm.
< Shell layer >
The shell of the anti-freezing modifier is formed by oxide particles, and the shell coats the core. In the present invention, the shell layer is used to encapsulate water-soluble metal salt particles as a core and has a strong binding force with the core, and thus can impart excellent sustained-release properties to an anti-icing coating and has excellent affinity and stability with a resin when used in the anti-icing coating.
Further, the thickness of the shell layer in the present invention is 10nm or more, and the upper limit of the thickness of the shell layer is not limited in general, and may be appropriately selected depending on the kind of the oxide particles and the actual use. Further, from the viewpoint of slow release and cost, the thickness of the shell layer in the present invention is more preferably 10nm to 200nm, still more preferably 15nm to 160nm, and still more preferably 20 to 130 nm. When the thickness of the shell layer is less than the above range, the slow release property of the anti-freezing modifier of the present invention tends to deteriorate. When the thickness of the shell layer is more than the above range, the sustained-release property is not further improved and the cost is increased.
In the present invention, there is no particular limitation on the kind of the oxide particles constituting the shell layer, as long as it can coat the core by means of the sol-gel method. Examples of such oxide particles include oxide particles of silicon, aluminum, phosphorus, boron, and transition metal elements, for example. They may be used alone or in a combination of two or more. Preferably, the oxide particles are silica particles or titania particles because of the wide range of applications and sources of these two oxides, low cost, and stable chemical and physical properties. For example, silica is non-toxic and harmless and has good biocompatibility, and titanium dioxide has excellent photocatalytic properties.
In addition, the particle diameter of the oxide particles constituting the shell layer of the present invention is preferably 2 to 100nm, more preferably 5 to 80nm, from the viewpoint of easier formation of the shell layer and more excellent sustained-release property.
Further, other elementary substances and compounds of elements can be doped into the shell layer of the anti-freezing modifier according to needs, so as to endow other functions to the shell layer, such as ultraviolet resistance, antistatic property, flame retardance and the like. In addition, the surface of the anti-freezing modifier (i.e. the outer surface of the shell layer facing the environment) can be subjected to various physical and chemical modification treatments as required, so as to obtain the performance of the surface of the anti-freezing modifier according to actual needs.
< method for producing core-shell type anticoagulation ice modifier >
The method for producing the core-shell type anticoagulation ice modifier of the present invention is actually a method for producing the same by a sol-gel method. The chemical process of the sol-gel method is that raw materials undergo hydrolysis reaction in a solvent to generate active monomers, the active monomers are polymerized to start to become sol, further gel with a certain space structure is generated, and the required material is prepared through drying and heat treatment. At present, the prior art has a technology of coating water-soluble metal salt by using a sol-gel method as an anti-freezing modifier.
Specifically, the manufacturing method of the present invention includes: uniformly dispersing water-soluble metal salt in an alcohol solvent, adding an alkaline catalyst, and optionally adding deionized water to obtain a pre-dispersion liquid (a pre-dispersion liquid preparation step); adding a precursor of oxide particles to the predispersion solution under stirring and carrying out a reaction (sol-gel forming step); the solid component was obtained by filtration, washed and dried (shell layer formation step).
The steps will be described in detail below.
< preparation step of Pre-Dispersion >
In the preparation step of the pre-dispersion liquid, the water-soluble metal salt is uniformly dispersed in an alcohol solvent, and then an alkaline catalyst and optionally deionized water are added to obtain the pre-dispersion liquid.
Specific examples of the alcoholic solvent used in the predispersion as the initial dispersion medium include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-pentanol, neopentyl alcohol, n-hexanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenethyl alcohol, ethylene glycol. They may be used alone or in a combination of two or more. From the viewpoint of further improving productivity, the alcohol solvent of the present invention is preferably one or more of methanol, ethanol, and isopropanol, and more preferably ethanol.
The details of the water-soluble metal salt particles have been described above and will not be described herein. From the viewpoint of easier formation of shell layers and further improvement of productivity, in the predispersion obtained in this step, the concentration of the dispersed water-soluble metal salt is preferably 5 to 50g/ml, preferably 10 to 45g/ml, more preferably 12 to 35g/ml, relative to the total amount of the alcoholic solvent as the initial dispersion medium.
In the present invention, there is no particular limitation on the sol-gel catalyst used, as long as it can cause a sol-gel process. Specific examples of the sol-gel catalyst include basic compounds such as ammonia, sodium hydroxide, potassium hydroxide and the like, and acidic compounds such as hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, acetic acid, phthalic acid and the like.
The sol-gel catalyst of the present invention is a basic compound from the viewpoint of easier formation of a shell layer. The pH of the predispersion formed in this step is preferably from 7.5 to 11.5, more preferably from 8.0 to 10.0.
In some preferred embodiments of the present invention, it is preferable to use ammonia water at a concentration of 25 to 28% from the viewpoint that the formation of the shell layer can be more easily controlled. In this case, the amount of the aqueous ammonia to be used is preferably 0.5 to 10% by volume, more preferably 0.8 to 6% by volume, and still more preferably 1 to 3% by volume, relative to the total amount of the alcoholic solvent as the initial dispersion medium. When the amount of aqueous ammonia is less than the above range, the oxide particle formation rate tends to be too slow. When the amount of the aqueous ammonia is more than the above range, the number of oxide particles free in the reaction system tends to be excessive, resulting in that the oxide particles tend to be difficult to coat on the water-soluble metal salt.
Further, the predispersion of the invention optionally comprises deionized water. The predispersion of the present invention preferably comprises deionized water from the viewpoint of easier formation of a shell layer and better sustained release of the resulting anti-freezing modifier. In this case, the deionized water of the present invention is used in an amount of preferably 2 to 20% by volume, and more preferably 3 to 16% by volume, relative to the total amount of the alcoholic solvent as the initial dispersion medium. When the amount of deionized water is less than the above range, hydrolysis of the precursor of the oxide particles described below tends to be insufficient. When the amount of deionized water is more than the above range, the amount of oxide particles free in the reaction system tends to be excessive, resulting in that the oxide particles tend to be difficult to coat on the water-soluble metal salt.
In this step, the deionized water may be added alone or in a mixture with an alcohol solvent, without any particular limitation. Preferably, the deionized water is added as a mixture with the alcoholic solvent, in which case the volume ratio of deionized water to alcoholic solvent (deionized water/alcoholic solvent) is preferably 0.2/10 to 12/10, more preferably 0.8/10 to 10/10, still more preferably 1/10 to 6/10. Examples of the alcohol solvent mixed with deionized water are the same as those listed for the alcohol solvent as the initial dispersion medium. In the present invention, more preferably, the alcohol solvent mixed with deionized water is the same as the above-mentioned alcohol solvent as the initial dispersion medium.
< Sol-gel Forming step >
In the sol-gel forming step, a precursor of the oxide particles is added to the predispersion obtained in the preceding step with stirring and the reaction is carried out.
The precursor of the oxide particles is not particularly limited. In theory, all precursors that can form oxides by the sol-gel method can be used. Specific examples of the precursor of the oxide particles include inorganic salts (including halides) or alkoxide compounds of silicon, aluminum, phosphorus, boron, and transition metal elements, and the like. Further, from the viewpoint of productivity and cost, an alkoxide compound of silicon or titanium; still more preferably, at least one selected from the group consisting of tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate and tetrabutyl silicate or at least one selected from the group consisting of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate and tetrabutyl titanate is used.
In general, the amount of the precursor of the oxide particles is not limited as long as the thickness of the obtained shell layer is 10nm or more. The amount of the precursor of the oxide particles may be appropriately selected depending on the kind of the precursor. In general, when the oxide particles are formed of silica, the mass ratio of the silica precursor to the water-soluble metal salt is preferably from 0.1/1 to 2/1, more preferably from 0.15/1 to 1.5/1, still more preferably from 0.2/1 to 1/1; and when the oxide particles are formed of titanium dioxide, the mass ratio of the titanium dioxide precursor to the water-soluble metal salt is preferably 0.08/1 to 1.2/1, more preferably 0.1/1 to 1/1, still more preferably 0.15/1 to 0.8/1.
In this step, the precursor of the oxide particles may be added alone or in a mixture with an alcohol solvent. Preferably, the precursor of the oxide particles is added in the form of a mixture with an alcohol solvent, in which case the volume ratio of the precursor of the oxide particles to the alcohol solvent is preferably 0.2/10 to 12/10, more preferably 0.8/10 to 10/10, still more preferably 1/10 to 6/10. Examples of the alcohol solvent mixed with the precursor of the oxide particles are the same as those listed for the alcohol solvent as the initial dispersion medium described above. In the present invention, it is more preferable that the alcohol solvent to be mixed with the precursor of the oxide particles is the same as the alcohol solvent as the initial dispersion medium.
The manner of adding the precursor of the oxide particles is not particularly limited, and the precursor may be added in one step or in portions. Preferably, in the present invention, the precursor of the oxide particles is added in one step.
In the present invention, after the precursor of the oxide particles is added, hydrolysis-polycondensation reaction occurs, thereby forming a gel. The reaction temperature is preferably 20 to 60 ℃ and more preferably room temperature from the viewpoint of ease of processing. The reaction time varies depending on the reaction temperature, and is preferably 6 to 24 hours, more preferably 8 to 16 hours.
< step of Forming Shell layer >
In the shell layer forming step, after the completion of the aforementioned hydrolysis-polycondensation reaction, a solid component is obtained by filtration, and washing and drying are carried out.
The filtration apparatus used in this step is not particularly limited, and conventionally known apparatuses for solid-liquid separation may be used.
The solid component obtained by filtration needs to be washed to remove unreacted raw materials, uncoated oxide particles and the sol-gel catalyst component. The washing is preferably carried out using the same alcohol solvent as the above-mentioned initial dispersion medium.
The drying temperature is not particularly limited, but is usually 20 to 98 ℃, preferably 20 to 60 ℃, and more preferably room temperature from the viewpoint of productivity.
< other steps >
In addition to the above steps, the method for producing an anticoagulation ice-modifying agent of the present invention may further comprise, as needed, classifying, metering, packaging, etc. the obtained anticoagulation ice-modifying agent.
Application of core-shell type anti-icing modifier
The core-shell type anti-freezing modifier can be used in anti-freezing coatings for various asphalt pavements, so that the formed anti-freezing coatings are endowed with hydrophobicity and anti-freezing property. Most preferably, when the core-shell type anti-freezing modifier of the present invention is used in the anti-freezing coating material of the present invention, the anti-freezing coating layer formed from the anti-freezing coating material can have excellent anti-freezing property, hydrophobicity, sustained release property and long service life.
< anti-Ice-coagulation coating >)
The anti-freezing coating of the invention can form an anti-freezing coating after being coated on the asphalt pavement and solidified.
Specifically, the anti-freezing coating comprises 10-70 parts by mass of asphalt, 0.5-5.0 parts by mass of a curing catalyst and 10-55 parts by mass of the core-shell type anti-freezing modifier relative to 100 parts by mass of an organic silicon material. 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 anti-freezing coating, the physical and chemical actions (affinity) between the anti-freezing modifier and other components are good, so that the anti-freezing modifier is not easy to damage in use and can keep the anti-freezing 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.
The core-shell type anticoagulant ice modifier of the present invention has been described in detail above, and thus will not be described in detail herein. It is to be noted that the content of the core-shell type anticoagulation ice 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 core-shell type anti-icing modifier is more than the above range, the amount of the anti-icing component (water-soluble metal salt) released during use tends to be excessively large, resulting in a negative effect on the environment. When the content of the core-shell type anti-icing modifier is less than the above range, the anti-icing property tends to deteriorate.
The following will describe in detail the other components constituting the anti-freezing ice coating material of the present invention, in addition to the above-mentioned core-shell type anti-freezing modifier.
< Silicone-based Material >
In the invention, when the organic silicon material is used for the anti-icing coating, the anti-icing coating formed after curing has strong binding force with the asphalt pavement, and simultaneously provides good hydrophobicity and affinity with the core-shell type anti-icing modifier, thereby prolonging the service life and improving the anti-icing property.
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 230 VP、
PN 100、
CONCENTRATE、
NFS、
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 anti-ice-freezing coating material, there is excellent affinity between the anti-ice-freezing coating layer and the asphalt pavement after coating is maintained in a dark hue. In addition, the impact resistance of the anti-ice coating is improved due to the plasticity of the asphalt.
The kind of asphalt used in the anti-freezing 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 impact resistance and hydrophobicity of the anti-ice coating layer, the content of the pitch 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 anti-freezing coating tends to be deteriorated, and the color of the anti-freezing coating tends to be excessively light to cause a reduction in the safety of the asphalt pavement. When the content of the asphalt is more than the above range, the hydrophobicity and wear resistance of the anti-ice coating layer tend to deteriorate. In addition, either too high or too low a pitch content tends to reduce the service life of the anti-icing coating.
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 IJGE 20.
< curing catalyst >
In the invention, the curing catalyst is used for crosslinking and curing the anti-freezing 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 anti-freezing coating of the invention can also comprise a filler, thereby further improving the strength and the anti-sliding property of the anti-freezing coating. 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.
In the case where the anti-ice-freezing coating material of the present invention contains a filler, the anti-ice-freezing coating material may further include a silane coupling agent to improve the affinity between the filler and the silicone-based material and to improve the dispersibility of the filler. Silane coupling agents of the present invention are known in the art, and examples thereof include, without limitation, vinyltris (β -methoxyethoxy) silane, γ -methacryloxypropyltrimethoxysilane (KH-570), γ -methacryloxypropyltriethoxysilane, γ -methacryloxypropyltripropoxysilane, γ -methacryloxyethyltrimethoxysilane, γ -methacryloxyethyltriethoxysilane, γ -methacryloxyethyltripropoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, N- β - (aminoethyl) γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane (KH-550), and mixtures thereof, Gamma-aminopropyltripropoxysilane, gamma-mercaptopropyltrimethoxysilane (KH-590), gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltripropoxysilane, gamma- (2, 3-glycidoxy) propylmethyldimethoxysilane, gamma- (2, 3-glycidoxy) propylmethyldiethoxysilane, gamma- (2, 3-glycidoxy) propylmethyldipropoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560), gamma- (2, 3-glycidoxy) propyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltripropoxysilane, gamma-glycidoxypropyltriisopropenoxysilane, gamma-glycidoxypropylmethyldiisopropenoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldiisopropenoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldiisopropenoxysilane, gamma-glycidyloxy-hydroxysilane, gamma-glycidyloxy-beta-glycidyloxy-beta-glycidyloxy-or-glycidyloxy-gamma-glycidyloxy-one-2, gamma-glycidyloxy-one-beta-glycidyloxy-one-beta-one-methyl-beta-one-methyl-beta-methyl-ethyl-methyl-ethyl-, Michael addition products of (meth) acryloylsilanes and aminosilanes, reaction products of epoxysilanes and aminosilanes, 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 anti-freezing coating material 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 dispersing 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 of anti-Ice coating >
The anti-icing coating of the present invention can be obtained by mixing an organic silicon material, asphalt, a silane coupling agent, a catalyst, the core-shell type anti-icing modifier of the present invention, and a filler, a silane coupling agent and the other components described above as required. 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 Ice-resistant coating >
The curing temperature of the anti-ice coating of the present invention is not particularly limited. Preferably, the curing of the anti-ice coating of the present invention is typically carried out at ambient temperature for outdoor construction needs.
Examples
Embodiments of the present invention will be illustrated below by way of examples, but the present invention is not limited to these specific examples. Unless otherwise specified, the term "parts" means "parts by mass", and "%" means "% by mass".
An anti-freezing modifier was prepared in the following production example.
Production example 1
Weighing 4g of industrial sodium chloride, adding the industrial sodium chloride into a 100mL conical flask, adding 30mL of absolute ethyl alcohol, and then carrying out ultrasonic dispersion for 10 min; measuring 0.5mL of ammonia water and 10mL of absolute ethyl alcohol by using a liquid transfer gun, adding into a small beaker, uniformly dispersing, adding into a conical flask, and uniformly stirring and dispersing; and then measuring 1.5mL of tetraethyl silicate and 10mL of absolute ethyl alcohol by using a liquid transfer gun, adding into a small beaker, adding into a conical flask after uniformly dispersing, sealing the container, and stirring at room temperature for reaction for 12 hours. After the reaction is finished, filtering, washing with alcohol and drying to obtain NaCl/SiO2Core-shell compositeParticles. Characterization was performed using SEM.
Production example 2
Weighing 4g of industrial sodium chloride, adding the industrial sodium chloride into a 100mL conical flask, adding 30mL of absolute ethyl alcohol, and then carrying out ultrasonic dispersion for 10 min; measuring 1.0mL of deionized water, 0.5mL of ammonia water and 10mL of absolute ethyl alcohol, adding into a small beaker, uniformly dispersing, adding into a conical flask, and uniformly stirring and dispersing; and then measuring 1.5mL of tetraethyl silicate and 10mL of absolute ethyl alcohol by using a liquid transfer gun, adding into a small beaker, adding into a conical flask after uniformly dispersing, sealing the container, and stirring at room temperature for reaction for 12 hours. After the reaction is finished, filtering, washing with alcohol and drying to obtain NaCl/SiO2Composite particles. Characterization was performed using SEM.
Production example 3
NaCl/SiO was prepared in the same manner as in production example 2, except that 2.0mL of deionized water was measured out2Core-shell composite particles.
Production example 4
NaCl/SiO was prepared in the same manner as in production example 2, except that 3.0mL of deionized water was measured out2Core-shell composite particles.
Production example 5
NaCl/SiO was prepared in the same manner as in production example 2, except that 1.0mL of tetraethyl silicate was measured out2Core-shell composite particles.
Production example 6
NaCl/SiO was prepared in the same manner as in production example 2, except that 2.0mL of tetraethyl silicate was measured out2Core-shell composite particles.
Production example 7
NaCl/SiO was prepared in the same manner as in production example 2, except that 0.2mL of aqueous ammonia was measured out2Core-shell composite particles.
Production example 8
NaCl/SiO was prepared in the same manner as in production example 2, except that 1.5mL of aqueous ammonia was measured out2Core-shell composite particles.
Production example 9
NaCl/SiO was prepared in the same manner as in production example 2, except that 0.5mL of tetraethyl silicate was measured out2Core-shell composite particles.
Comparative production example 1
4g of industrial sodium chloride and 5g of silane coupling agent KH-550 are mixed under heating to obtain the silane coupling agent coated anti-freezing ice modifier.
Comparative production example 2
Adding 4g of industrial sodium chloride into water, heating and stirring, adding 2g of zeolite after dissolving, fully mixing and evaporating all water to obtain the zeolite-loaded anti-freezing ice modifier.
Various anti-ice coatings and coatings formed therefrom were prepared in the following examples.
Example 1
Adding 40 parts of emulsified asphalt with a solid content of 50% into 100 parts of organic silicon emulsion with a solid content of 50% and stirring at the rotating speed of 200rpm for 10min, adding 16 parts of core-shell type anti-freezing ice modifier prepared in production example 2 and stirring at the rotating speed of 200rpm for 15min, adding 3 parts of silane coupling agent, simultaneously adding 1.0 part of dibutyltin dilaurate and stirring at the rotating speed of 300rpm for 20min, and finally adding 10 parts of 40-mesh carborundum. Obtaining the hydrophobic slow-release anti-freezing organic silicon coating.
Example 2
A silicone coating was obtained in the same manner as in example 1, except that the core-shell type anti-icing modifier in example 1 was replaced with the core-shell type anti-icing modifier prepared in production example 1.
Example 3
A silicone coating was obtained in the same manner as in example 1, except that the core-shell type anti-icing modifier in example 1 was replaced with the core-shell type anti-icing modifier prepared in production example 9.
Comparative example 1
A silicone coating was obtained in the same manner as in example 1, except that the core-shell type anti-icing 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 core-shell type anti-icing modifier in example 1 was replaced with the anti-icing modification 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 core-shell type anti-icing modifier in example 1 was replaced with the anti-icing 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 core-shell type anti-icing 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 core-shell type anti-icing 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 core-shell type anti-icing 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.
Performance testing
Hydrophobicity of anti-Ice modifier
Since the surface of the anti-freezing modifier is irregular, the present invention tests the hydrophobicity of the anti-freezing modifier by the following method commonly used in the industry.
Step 1: taking out the anti-freezing modifier, piling the anti-freezing modifier on the surface of the filter paper in a conical shape, pressing down from the vertex of the conical shape, and pressing the conical pile out of a smooth inner concave surface;
step 2: taking deionized water by using a 0.5ml dropper, and dripping water drops from the lowest point of the concave surface;
and step 3: the time for which the water droplet stayed on the concave surface without permeating the anti-freezing modifier was recorded.
The anti-icing agents in the respective production examples and comparative production examples were evaluated based on the following criteria, and the results are shown in table 2.
Very good: the retention time is more than 5min,
o: the retention time is less than 5min and more than 3min,
and (delta): the retention time is less than 1min and more than 20 seconds,
x: the residence time was less than 20 seconds.
TABLE 2
Hydrophobicity of the coating
Hydrophobicity of the anti-icing coating layers formed from the anti-icing coating materials in each of examples and comparative examples can be 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, an anti-freezing coating is sprayed onto the surface of a glass slide and cured to form an anti-freezing coating, and thereafter, water droplets are dropped onto the surfaces of an uncoated glass slide and a glass slide having an anti-freezing coating, respectively, and photographs are taken in comparison with the case of a static contact angle. Specific results regarding the contact angles of the anti-ice coatings in the respective examples and comparative examples are shown in table 3.
The test results for the coating of example 1 are shown in fig. 4. 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. 5 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 anti-ice-freezing paint of example 1, respectively. As can be seen from FIG. 5, 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 anti-icing 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 anti-freezing 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 0.4-0.6kg/m2。
Step 2: after the coating is solidified to coat, simulating the process of rainfall and snowfall in winter, and adding a certain amount of water (the amount of water is equivalent to the rainfall and snowfall amount in one area about once) on the surface of the test piece. It was then placed in a-15 ℃ cryostat to simulate winter climatic conditions.
And step 3: and taking out the test piece after 3 hours, simulating the impact effect of an automobile tire on the road surface, lightly knocking the ice layer, and then observing the cracking condition of the ice layer and the combination condition of the ice blocks and the surface of the test piece.
Because the anti-freezing principle of the anti-freezing coating is that the ice layer is broken by the action of the load of the vehicle, the ice layer is separated from the road surface, the freezing point is lowered, and 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 and the degree of falling off from the test piece after lightly tapping the ice layer.
Fig. 6 shows the deicing effect of the coating layer formed of the reference paint and the coating layer formed of the anti-ice-freezing paint of example 1. As shown in fig. 6, 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 by a light tap. With this as a reference, evaluation was performed based on the following criteria.
O: after knocking, the ice layer is loosened and broken and completely falls off,
and (delta): after knocking, 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: similarly to step 1 in the test of anti-icing property, the anti-icing paint prepared in examples and comparative examples was painted on the test piece.
Step 2: after the coating is dried and coated, 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, lightly knocking the ice layer, and then 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, step 4: and if the ice layer is fragile (reaches a level above delta 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.
O: the process can be repeated for more than 10 times,
and (delta): it may 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 3.
TABLE 3
| Example numbering | Contact angle (°) | Resistance to ice condensation | Sustained release property |
| Example 1 | 95.6 | ○ | ○ |
| Example 2 | 95.2 | ○ | △ |
| Example 3 | 93.0 | ○ | ○ |
| Comparative example 1 | 91.5 | ○ | × |
| Comparative example 2 | 92.4 | △ | × |
| Comparative example 3 | 91.5 | △ | × |
| Example 4 | 95.4 | ○ | ○ |
| Comparative example 4 | 95.6 | × | × |
| Comparative example 5 | 96.4 | ○ | ○ |
| Example 5 | 97.0 | ○ | ○ |
| Comparative example 6 | 89.2 | ○ | △ |
| Comparative example 7 | 97.9 | ○ | × |
As shown in table 3, the coatings formed by examples 1 to 5 satisfying the present invention have excellent hydrophobicity, anti-icing property, and sustained-release property. In addition, the coatings formed from examples 1 to 5 satisfying the present invention did not have significant salt precipitation during the test for evaluating the sustained release property, and the coatings were not damaged, i.e., the coatings could be used for a long time.
As shown in table 3, although the coatings formed by comparative examples 1 to 3 satisfying the present invention have good hydrophobicity, anti-freezing property and sustained-release property are inferior compared to the effect of the present invention.
In comparative example 4, the amount of the anti-freezing modifier used was too small, and therefore, the anti-freezing property and the sustained-release property were poor. Although the coating layer formed from the coating material of comparative example 5 has good hydrophobicity, anti-icing property and sustained-release property, since the amount of the anti-icing modifier in comparative example 5 is too large, white salt precipitation is observed gradually on the surface of the test piece when repeated tests are performed in the evaluation of sustained-release property, which causes environmental pollution in actual use; in addition, excessive use of anti-icing agents can result in excessive costs.
When the emulsified asphalt is excessive (comparative example 6), the bonding force of the coating to the road surface is insufficient and the hydrophobicity is reduced; on the other hand, when the emulsified asphalt is too small (comparative example 7), the external impact resistance of the coating layer is insufficient. Therefore, the sustained release property in both cases is deteriorated, and the service life is also deteriorated.
The above embodiments are merely examples provided for clarity of explanation and are not intended to limit the present invention. It will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the present invention.
Claims (6)
1. A core-shell type anticoagulation ice modifier, which is characterized by comprising a core and a shell, wherein the core is a water-soluble metal salt particle, the shell is formed by an oxide particle, and the shell coats the core; the thickness of the shell layer is 10nm-200nm, the size of the water-soluble metal salt particles is 5-20 mu m, and the core-shell type anti-icing modifier is obtained by a manufacturing method comprising the following steps:
uniformly dispersing water-soluble metal salt in an alcohol solvent serving as an initial dispersion medium, adding a basic catalyst, and optionally adding deionized water to obtain a pre-dispersion liquid, wherein the concentration of the water-soluble metal salt is 5-50g/ml relative to the total amount of the alcohol solvent, the pH of the pre-dispersion liquid is 8.0-10.0, and the usage amount of the deionized water is 2-20 vol% relative to the total amount of the alcohol solvent;
adding a precursor of oxide particles into the pre-dispersion liquid under stirring, and carrying out sol-gel reaction;
filtering to obtain a solid component, and washing and drying;
the oxide particles are silica particles or titania particles,
the water-soluble metal salt is at least one selected from sodium chloride, calcium chloride, magnesium chloride, calcium acetate, magnesium acetate and potassium acetate,
the alkaline catalyst is at least one selected from ammonia water, sodium hydroxide and potassium hydroxide.
2. A method for producing the core-shell type anti-icing modifier according to claim 1, comprising:
uniformly dispersing water-soluble metal salt in an alcohol solvent serving as an initial dispersion medium, adding a basic catalyst, and optionally adding deionized water to obtain a pre-dispersion liquid, wherein the concentration of the water-soluble metal salt is 5-50g/ml relative to the total amount of the alcohol solvent, the pH of the pre-dispersion liquid is 8.0-10.0, and the usage amount of the deionized water is 2-20 vol% relative to the total amount of the alcohol solvent;
adding a precursor of oxide particles into the pre-dispersion liquid under stirring, and carrying out sol-gel reaction;
filtering to obtain a solid component, and washing and drying;
the oxide particles are silica particles or titania particles,
the water-soluble metal salt is at least one selected from sodium chloride, calcium chloride, magnesium chloride, calcium acetate, magnesium acetate and potassium acetate,
the alkaline catalyst is at least one selected from ammonia water, sodium hydroxide and potassium hydroxide.
3. An anti-icing coating, comprising: 10 to 70 parts by mass of asphalt, 0.5 to 5.0 parts by mass of a curing catalyst, and 10 to 55 parts by mass of the core-shell type anti-icing modifier according to claim 1, based on 100 parts by mass of the silicone material.
4. The anti-freezing coating according to claim 3, wherein the silicone material is at least one selected from the group consisting of 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.
5. The anti-ice-freezing coating according to claim 3 or 4, further comprising a filler.
6. The anti-ice-freezing coating according to claim 5, further comprising a silane coupling agent.
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