CN112126329A - Spray-type water conservancy dam ice-pulling-resistant and wear-resistant polyurea coating and processing technology thereof - Google Patents
Spray-type water conservancy dam ice-pulling-resistant and wear-resistant polyurea coating and processing technology thereof Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
The invention provides a spray-coating type water conservancy dam anti-icing and wear-resistant polyurea coating, which belongs to the technical field of coating production and consists of a component A and a component B in a volume ratio of 1:1, wherein the component A comprises the following raw materials in parts by weight: 45-65 parts of isocyanate, 35-55 parts of polyether polyol and 10-20 parts of polydimethylsiloxane; the component B comprises the following raw materials in parts by weight: 40-70 parts of amino-terminated polyether, 10-50 parts of liquid amine chain extender, 10-50 parts of stearic acid modified nano aluminum oxide, 0-2 parts of dispersing agent, 0-2 parts of defoaming agent, 0-2 parts of antioxidant, 0-2 parts of thickening agent and 2-8 parts of pigment. The polyurea coating A component contains polydimethylsiloxane, the B component contains stearic acid modified nano alumina particles, the problems of wear resistance, ice pull resistance and aging resistance of a water conservancy dam polyurea coating in the prior art can be solved through a single polyurea coating without matching with finish paint, and the prepared super-hydrophobic coating is wide in applicability and high in stability; the polyurea coating has the advantages of simple processing technology, easily obtained raw materials and low cost.
Description
Technical Field
The invention relates to the technical field of paint production, in particular to a spray-type water conservancy dam ice-pulling-resistant and wear-resistant polyurea paint and a processing technology thereof.
Background
When the bottom of the dam and the channel runs under the conditions of high flow rate, large flow and high sand content for a long time, the erosion of the concrete surface is serious, and local exposed ribs appear, so that the stability and the service life of the channel are influenced; the concrete layer is aged and cracked, the seepage is increased, the freeze-thaw damage is caused, and the dam body and the channel surface are damaged.
Ice pull damage is mainly caused by the fact that ice adheres to the surface of an object (freezing force) and moves with the surface of the object during the melting process of the ice, and then upward or downward pulling force is generated on the object, and the effect of the force causes the object to be damaged. In the hydraulic engineering dam body in cold areas, in order to avoid the problem that the self stress of the dam body exceeds an allowable value and cracks appear due to the difference of the internal temperature and the external temperature of the dam body, thermal insulation materials are covered outside the dam body to carry out thermal insulation. In cold regions such as northeast or northwest of China, when the temperature is the coldest, the icing phenomenon occurs on the upstream water surface of the dam, the thickness of an ice layer reaches 1.3m, after the water level of a reservoir is reduced and changed, the ice layer can damage the heat insulation layer of the dam body by ice pulling, and the heat insulation layer of the existing dam body is spliced together, so that gaps exist between the spliced heat insulation layers, the heat insulation layer can be damaged and fall off in an accelerated manner under the action of ice pulling, the dam body can generate temperature cracks finally, potential safety hazards can occur on the dam body, the safe operation of the reservoir is affected, and after the problem occurs, the existing treatment scheme is complex, the construction is difficult, the maintenance cost is high, and the treatment effect is poor.
Polyurea coating (polyurea coatings) adopts a one-time coating process, no chain joint exists in any area, and the polyurea coating is a dust-free material polyurea coating and has the characteristics of strong adhesive force, friction resistance, strong hardness and the like; the polyurea coating has the characteristics of better corrosion resistance, water resistance and wear resistance, and is widely applied in many fields. However, the waterproof and wear-resistant polyurea coating special for the existing reservoir dam is insufficient in waterproof and wear-resistant performance, so that most of dam surfaces and spillways are worn due to the existence of a wear medium, and the use is influenced.
The Chinese patent with the application number of CN201910330039.2 and the invention name of 'a special waterproof wear-resistant polyurea coating for reservoir dams and a processing technology thereof' discloses a special waterproof wear-resistant polyurea coating for reservoir dams and a processing technology thereof, and modified polyaspartic ester is matched with isocyanate to ensure that the coating has better corrosion resistance, wear resistance, stability and the like. The polyaspartic ester polyurea does not contain benzene rings in the molecular structure, is similar to aliphatic polyurea, has excellent aging resistance, has adhesive force between aromatic polyurea and aliphatic polyurea, but does not increase wear-resistant performance groups in the view of the molecular structure, so that the simple polyaspartic ester polyurea can not meet the requirements of wear resistance and ice-pull resistance of a water conservancy dam.
For example, chinese patent with application number CN201910416309.1, entitled "heat preservation, seepage prevention, ice pulling prevention and protection system for dam in severe cold area" and construction method thereof discloses an anti-freezing, melting, heat preservation, ice pulling prevention and protection system for dam body, which is composed of anti-freezing, melting, heat preservation, ice pulling prevention and protection facilities respectively arranged on the upstream surface and the downstream surface of the dam body at both sides of the dam body. The protective facilities comprise an anti-freezing and anti-melting heat insulation layer, a reinforced layer and an anti-icing protective layer from inside to outside. The anti-icing protective layer is formed by a two-layer structure, the inner layer is a bi-component polyurea coating, and the outer layer is fluorine modified weather-resistant polyurea finish paint. The surface of the polyurea coating is coated with the fluorine modified weather-resistant finish paint with high weather resistance and strong hydrophobicity, the organic fluorine compound has low intermolecular cohesion, small molecular acting force between air and a polymer interface, low surface free energy and small surface friction coefficient, the organic fluorine polymer is endowed with excellent water resistance, oil resistance and wear resistance, and the freeze-bonding strength of ice can be reduced, so that the hydrophobic ice-phobic performance of the structure surface is enhanced. Although the freeze-bonding strength of ice can be reduced by the fluorine modified weather-resistant polyurea finish paint, polyurea is coated by the finish paint, and the advantage of polyurea wear resistance cannot be exerted, wherein the thickness of the fluorine modified finish paint is 0.2mm, the wear resistance is poor, and water flow scouring is not resisted; after the finish paint is stripped, the exposed polyurea has poor aging resistance and is easy to lose gloss and chalk.
In conclusion, the existing technical schemes cannot solve the problems of wear resistance and ice pull resistance at the same time, so that a new polyurea coating is urgently needed to be researched, and the problems of wear resistance, ice pull resistance and aging resistance of the polyurea coating for the water conservancy dam can be solved at the same time.
Disclosure of Invention
In view of the above, the invention provides a spray-coating type water conservancy dam ice-pull-resistant wear-resistant polyurea coating and a processing technology thereof, wherein the component A comprises polydimethylsiloxane, the component B comprises stearic acid modified nano alumina particles, and the polyurea coating does not need to be matched with finish paint, so that the problems of wear resistance, ice-pull resistance and aging resistance of the water conservancy dam polyurea coating in the prior art can be solved through a single polyurea coating, and the prepared super-hydrophobic coating has wide applicability and high stability; the polyurea coating has the advantages of simple processing technology, easily obtained raw materials and low cost.
In order to achieve the purpose, the invention provides the following technical scheme:
a spray-type water conservancy dam anti-icing wear-resistant polyurea coating comprises a component A and a component B, wherein the volume ratio of the component A to the component B is 1: 1;
wherein the component A comprises the following raw materials in parts by weight: 45-65 parts of isocyanate, 35-55 parts of polyether polyol and 10-20 parts of polydimethylsiloxane;
the component B comprises the following raw materials in parts by weight: 40-70 parts of amino-terminated polyether, 10-50 parts of liquid amine chain extender, 10-50 parts of stearic acid modified nano aluminum oxide, 0-2 parts of dispersing agent, 0-2 parts of defoaming agent, 0-2 parts of antioxidant, 0-2 parts of thickening agent and 2-8 parts of pigment.
Further, the isocyanate is one or more of 2, 6-toluene diisocyanate, 4 '-diphenylmethane diisocyanate, carbodiimide-uretonimine modified 4, 4' -diphenylmethane diisocyanate, 2,4 '-diphenylmethane diisocyanate, polymethine polyphenyl isocyanate, 4' -dicyclohexylmethane diisocyanate and isophorone diisocyanate.
Further, the polyether polyol is one of polyethylene glycol ether, polypropylene glycol ether, polypentaerythritol ether, polytetrahydrofuran ether glycol and polycaprolactone glycol, or a mixture of a plurality of copolymers.
Further, the amino-terminated polyether is difunctional amino-terminated polyether or trifunctional amino-terminated polyether.
Further, the liquid amine chain extender is one or more of diethyl toluene diamine, dimethyl sulfur toluene diamine, N '-di-sec-butyl methylene diphenylamine, 4' -diaminodiphenylmethane and 3,3 '-dichloro-4, 4' -diaminodiphenylmethane.
Further, the molar mass of the polydimethylsiloxane is 1000-4000 g/mol.
Furthermore, in the stearic acid modified nano-alumina, the grafting rate of stearic acid on the surface of the nano-alumina is 6-12%.
The invention also provides a processing technology of the spray-type water conservancy dam ice-pulling-resistant and wear-resistant polyurea coating, which comprises the following steps:
s1: preparation of component A
In an inert environment, stirring and heating the polyether polyol to 95-100 ℃, dehydrating for 5-7h under the vacuum degree of-0.1 MPa, relieving the vacuum, cooling to below 50 ℃, adding the isocyanate and the polydimethylsiloxane, reacting for 3-4h at (90 +/-5) DEG C, measuring the-NCO value after the reaction is finished, discharging, filtering and discharging;
s2: preparation of component B
1) Ultrasonically dispersing the stearic acid modified nano alumina into a part of amino-terminated polyether to prepare stearic acid modified nano alumina pre-pulping;
2) dispersing the pigment in a part of amino-terminated polyether, and grinding to prepare pigment pre-pulping;
3) sequentially adding the stearic acid modified nano-alumina pre-pulping, the pigment pre-pulping, the rest amino-terminated polyether, the liquid amine chain extender, the dispersant, the defoamer, the antioxidant and the thickener into a paint preparation tank, and stirring at a high speed for 25-30 minutes by using high-shear dispersion equipment to prepare the pigment modified nano-alumina paint;
and (3) uniformly mixing the component A and the component B in a volume ratio of 1:1 by a spraying machine, spraying the mixture on the surface of the base material of the hydraulic dam, and curing.
The spray-type water conservancy dam anti-icing and wear-resistant polyurea coating provided by the invention has the advantages that the component A contains polydimethylsiloxane, the component B contains stearic acid modified nano alumina particles, finish paint does not need to be matched, the problems of wear resistance, icing resistance and aging resistance of the water conservancy dam polyurea coating in the prior art can be solved through a single polyurea coating, the water contact angle of the prepared polyurea coating is 150 degrees, and good super-hydrophobicity is kept; the icing force is less than 20N, and the ice adhesion on the surface of the coating is small; the wear resistance can reach 750g/500r, and g is less than or equal to 8 mg. Therefore, the anti-ice-pulling and wear-resistant polyurea coating for the manual blade coating type water conservancy dam has the advantages of good wear resistance, ice-pulling resistance and aging resistance, wide applicability and high stability. In addition, the polyurea coating has the advantages of simple processing technology, easily obtained raw materials and low cost.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a spray-coating type anti-icing and wear-resistant polyurea coating for a water conservancy dam, which consists of a component A and a component B, wherein the volume ratio of the component A to the component B is 1: 1;
wherein the component A comprises the following raw materials in parts by weight: 45-65 parts of isocyanate, 35-55 parts of polyether polyol and 10-20 parts of polydimethylsiloxane;
the component B comprises the following raw materials in parts by weight: 40-70 parts of amino-terminated polyether, 10-50 parts of liquid amine chain extender, 10-50 parts of stearic acid modified nano aluminum oxide, 0-2 parts of dispersing agent, 0-2 parts of defoaming agent, 0-2 parts of antioxidant, 0-2 parts of thickening agent and 2-8 parts of pigment.
A large number of hydrogen bonds are formed inside the molecules of the polytetrahydrofuran polyol type polyurea material, when the surface of the coating is rubbed, plastic deformation can occur, and at the moment, the hydrogen bonds between the surface layer and the middle layer can absorb energy until the hydrogen bonds break. Therefore, the polytetrahydrofuran polyol type polyurea material has excellent wear resistance, and is modified by polydimethylsiloxane, and the friction coefficient of the material is reduced because silicon atoms on the surface of the enriched material play a role in lubrication. In addition, the bond energy of the silicon-oxygen bond is very large, the thermal stability of the material is improved, and when the material is abraded, more energy is needed to break molecular chains, so that the abrasion resistance is improved.
Hydroxyl on the surface of the nano aluminum oxide and carboxyl of stearic acid are subjected to esterification reaction similar to organic acid and organic alcohol, so that the polarity of the nano aluminum oxide is changed, and the modified nano aluminum oxide can be uniformly dispersed in the coating without agglomeration. Through adding stearic acid modified nanometer alumina particles, the film-forming property of the polyurea surface is damaged, bulges formed by accumulating the nanometer particles appear, the surface becomes rough, and the multi-level micro-nanometer coarse structures can intercept more air, so that the contact area between water drops and the surface is reduced, and the polyurea surface has super-hydrophobic property. The coating after film formation has the characteristics of excellent smoothness, high water contact angle, excellent weather resistance and the like. The water is easy to roll and slide under the action of natural external force, so that the water hanging amount before ice formation (ice coating) is reduced; can inhibit or delay the formation of ice crystals on the surface of the material; the adhesive force between the ice crystals and the contact interface can be reduced; reduce the meteorological disasters to the engineering field caused by the ice coating phenomenon after thawing.
In the component A, the isocyanate is one or more of 2, 6-toluene diisocyanate, 4 '-diphenylmethane diisocyanate, carbodiimide-uretonimine modified 4, 4' -diphenylmethane diisocyanate, 2,4 '-diphenylmethane diisocyanate, polymethine polyphenyl isocyanate, 4' -dicyclohexylmethane diisocyanate and isophorone diisocyanate. The polyether polyol is one or a mixture of a plurality of polyethylene glycol ethers, polypropylene glycol ethers, polypentaerythritol ethers, polytetrahydrofuran ether glycols and polycaprolactone glycols, or a copolymer of a plurality of copolymers, or a mixture of a plurality of copolymers.
In the component B, the amino-terminated polyether is bifunctional amino-terminated polyether or trifunctional amino-terminated polyether. The liquid amine chain extender is one or more of diethyl toluene diamine, dimethyl sulfur toluene diamine, N '-di-sec-butyl methylene diphenylamine, 4' -diaminodiphenylmethane and 3,3 '-dichloro-4, 4' -diaminodiphenylmethane.
The stearic acid modified nano aluminum oxide has the advantages that the particle size of the stearic acid modified nano aluminum oxide influences the size of protrusions on the surface of the polyurea coating, so that the hydrophobic performance of the surface of the polyurea coating is influenced, in the stearic acid modified nano aluminum oxide, the grafting rate of stearic acid on the surface of the nano aluminum oxide is 6-12%, the dispersibility of the stearic acid modified nano aluminum oxide in a solvent is improved, the nano aluminum oxide before modification is hydrophilic and oleophobic, but the stearic acid modified nano aluminum oxide is oleophilic and hydrophobic. The molecular weight of the polyol is controlled to be 500-4000, the functionality is controlled to be 2-4, and the molar mass of the polydimethylsiloxane is controlled to be 1000-4000g/mol, because the raw materials are easy to obtain, and the viscosity of the prepared polyurea coating is lower than 2000mPa & S, so that the polyurea coating is easy to spray and construct.
Examples
The processing process of the spray-type water conservancy dam ice-pulling-resistant wear-resistant polyurea coating comprises the following steps:
s1: preparation of component A
In an inert environment, 44 parts of polypropylene oxide ether glycol with the molecular weight of 1000 and the functionality of 2 are stirred and heated to 95-100 ℃, dehydrated for 5 hours under the vacuum degree of-0.1 MPa, relieved of vacuum, cooled to below 50 ℃, added with 15 parts of 2,4 '-diphenylmethane diisocyanate, 40 parts of 4, 4' -diphenylmethane diisocyanate and 25 parts of polydimethylsiloxane, reacted for 3 hours at 90 ℃, and after the reaction is finished, the-NCO value is measured, and then the materials are discharged, filtered and discharged;
s2: preparation of component B
1) Ultrasonically dispersing 20 parts of stearic acid modified nano alumina in 20 parts of amino-terminated polyether D2000 to prepare stearic acid modified nano alumina pre-pulping;
2) preparing a mixture of 5 parts of pigment and 10 parts of amino-terminated polyether D2000, and dispersing the mixture into pigment pre-pulping by using grinding equipment such as a sand mill;
3) adding the stearic acid modified nano-alumina pre-pulping, the pigment pre-pulping, 15 parts of amino-terminated polyether, 10 parts of chain extender, 2 parts of dispersant, 2 parts of defoaming agent, 2 parts of antioxidant and 2 parts of thickener into a paint preparation tank, and stirring at high speed for 25-30 minutes by using high-shear dispersion equipment to prepare the nano-alumina paint;
and (3) uniformly mixing the component A and the component B in a volume ratio of 1:1 by a spraying machine, spraying the mixture on the surface of the base material of the hydraulic dam, and curing.
The spray-type water conservancy dam ice-pulling-resistant and wear-resistant polyurea coating is placed in an environment with the temperature of (25 +/-2) DEG C and the humidity of (50 +/-5)%, and after 7 days of maintenance, the test performance is as follows: abrasion resistance (750g/500r)), g is less than or equal to 8mg, the water contact angle is 140 degrees, the icing force is 12N, and the drawing strength is 3.2 MPa.
The spray-type water conservancy dam anti-icing and wear-resistant polyurea coating provided by the invention has the advantages that the component A contains polydimethylsiloxane, the component B contains stearic acid modified nano alumina particles, finish paint does not need to be matched, the problems of wear resistance, icing resistance and aging resistance of the water conservancy dam polyurea coating in the prior art can be solved through a single polyurea coating, the water contact angle of the prepared polyurea coating is 150 degrees, and good super-hydrophobicity is kept; the icing force is less than 20N, and the ice adhesion on the surface of the coating is small; the wear resistance can reach 750g/500r, and g is less than or equal to 8 mg. Therefore, the anti-ice-pulling and wear-resistant polyurea coating for the manual blade coating type water conservancy dam has the advantages of good wear resistance, ice-pulling resistance and aging resistance, wide applicability and high stability. In addition, the polyurea coating has the advantages of simple processing technology, easily obtained raw materials and low cost.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. The spray-type water conservancy dam anti-icing wear-resistant polyurea coating is characterized by comprising a component A and a component B, wherein the volume ratio of the component A to the component B is 1: 1;
wherein the component A comprises the following raw materials in parts by weight: 45-65 parts of isocyanate, 35-55 parts of polyether polyol and 10-20 parts of polydimethylsiloxane;
the component B comprises the following raw materials in parts by weight: 40-70 parts of amino-terminated polyether, 10-50 parts of liquid amine chain extender, 10-50 parts of stearic acid modified nano aluminum oxide, 0-2 parts of dispersing agent, 0-2 parts of defoaming agent, 0-2 parts of antioxidant, 0-2 parts of thickening agent and 2-8 parts of pigment.
2. The spray-type water conservancy dam anti-icing and wear-resistant polyurea coating according to claim 1, wherein the isocyanate is one or more of 2, 6-toluene diisocyanate, 4 '-diphenylmethane diisocyanate, carbodiimide-uretonimine modified 4, 4' -diphenylmethane diisocyanate, 2,4 '-diphenylmethane diisocyanate, polymethine polyphenyl isocyanate, 4' -dicyclohexylmethane diisocyanate and isophorone diisocyanate.
3. The spray-type water conservancy dam anti-icing and wear-resistant polyurea coating according to claim 1, wherein the polyether polyol is one of polyethylene glycol ether, polypropylene glycol ether, polypentaerythritol ether, polytetrahydrofuran ether glycol and polycaprolactone glycol, or a mixture of a plurality of the polyether glycol, the polypropylene glycol ether, the polytetrahydrofuran ether glycol and the polycaprolactone glycol.
4. The spray-type water conservancy dam ice-pull-resistant and wear-resistant polyurea coating according to claim 1, wherein the amino-terminated polyether is a di-functional amino-terminated polyether or a tri-functional amino-terminated polyether.
5. The spray-type water conservancy dam ice-pulling-resistant and wear-resistant polyurea coating according to claim 1, wherein the liquid amine chain extender is one or more of diethyl toluene diamine, dimethyl sulfide toluene diamine, N '-di-sec-butyl methylene diphenylamine, 4' -diaminodiphenylmethane, and 3,3 '-dichloro-4, 4' -diaminodiphenylmethane.
6. The spray-type water conservancy dam ice-pulling-resistant and wear-resistant polyurea coating as claimed in claim 1, wherein the molar mass of the polydimethylsiloxane is 1000-4000 g/mol.
7. The spray-type water conservancy dam ice-pulling-resistant and wear-resistant polyurea coating according to claim 1, wherein in the stearic acid-modified nano alumina, the grafting ratio of stearic acid on the surface of the nano alumina is 6-12%.
8. A process for preparing the ice-pulling-resistant and wear-resistant polyurea coating for the spraying-type water conservancy dam as claimed in any one of claims 1 to 7, which comprises the following steps:
s1: preparation of component A
In an inert environment, stirring and heating the polyether polyol to 95-100 ℃, dehydrating for 5-7h under the vacuum degree of-0.1 MPa, relieving the vacuum, cooling to below 50 ℃, adding the isocyanate and the polydimethylsiloxane, reacting for 3-4h at (90 +/-5) DEG C, measuring the-NCO value after the reaction is finished, discharging, filtering and discharging;
s2: preparation of component B
1) Ultrasonically dispersing the stearic acid modified nano alumina into a part of amino-terminated polyether to prepare stearic acid modified nano alumina pre-pulping;
2) dispersing the pigment in a part of amino-terminated polyether, and grinding to prepare pigment pre-pulping;
3) sequentially adding the stearic acid modified nano-alumina pre-pulping, the pigment pre-pulping, the rest amino-terminated polyether, the liquid amine chain extender, the dispersant, the defoamer, the antioxidant and the thickener into a paint preparation tank, and stirring at a high speed for 25-30 minutes by using high-shear dispersion equipment to prepare the pigment modified nano-alumina paint;
and (3) uniformly mixing the component A and the component B in a volume ratio of 1:1 by a spraying machine, spraying the mixture on the surface of the base material of the hydraulic dam, and curing.
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