Corrosion resistant and heat-retention coat based 0n hollow microsphere mixture

FIELD: pipeline heat insulation in civil and industrial building.

SUBSTANCE: coating composition includes 5-95 vol.% of polymeric binder and 5-95 vol.% of hollow microspheres. At least one composition layer is coated onto substrate and dried. Said polymeric binder contains 10-90 % of (co)polymer selected from acrylate homopolymer, styrene-acrylate copolymer, butadiene-styrene copolymer, polyvinylchloride, polyurethane, vinylacetate polymer or copolymer or mixture thereof. Binder also contains 10-90 vol.% of water and surfactant mixture. hollow microspheres have particle size of 10-500 mum and bulk density of 50-650 kg/m3, and made from glass, ceramic, polymers, sol or mixture thereof.

EFFECT: improved corrosion resistance and heat insulation of coated substrate; increased adhesion properties.

5 cl, 1 tbl, 1 ex, 3 dwg

 

The scope to which the invention relates.

High quality corrosion and heat-protective coating for a number of applications is of paramount importance. For example, when solving the problem of thermal insulation of pipelines and water supply is extremely important to ensure long-lasting protection of the pipe from external corrosion, because it is the main factor limiting their useful life. Just as important are such coatings and to protect any building structures made of metal, wood, plastic, from the harmful effects of sunlight, rainfall, etc. At the same time, the task of maintaining heat in residential and industrial building is definitely one of the paramount, and the huge resources are being allocated. To solve both the first and second tasks of modern process thought offers a wide range of solutions. By insulating materials, actively offer at the present time, in addition to well-known mineral and basalt Wat the use of different foamed polymeric materials, such as foamed polystyrene, polyethylene, polyurethane, polypropylene, etc. as materials for corrosion protection offers a variety of painting materials (water dispersion, coating materials on the body of the ical solvents), and protection of metal surfaces metal, resistant to corrosion, such as electrolytic zinc plating. Materials which would have had the joint effect of protecting surfaces from corrosion and thus would contribute to the conservation of heat and has a high adhesion property at the present time, practically does not exist.

The level of technology

In the patent of Russian Federation №93052300 (1996.07.20) (applicants and inventors: Dubin IB, Asiants A.P., Laptev I.I., Mansurov M.N., Sarkisov EI) proposed to use glass microspheres as a filler to obtain zamknutosti composition, with full resistance and high thermal insulation properties, high mechanical strength and a coefficient of linear expansion that is compatible with the metal of the pipe. In this case, the use of such coatings requires the preparation of a liquid mixture, a modified epoxy resin ED-20, glass microspheres, hardener - polyethylenepolyamine (PEPA), plasticizer of polyisobutylene And-200 and other components immediately before use, because otherwise pre-prepared mixture will harden quickly, not allowing to apply it to the surface. This fact is not very convenient from a technological point of view, in addition, such a coating cannot withstand direct the spray contact with water. In addition, the ability of the finished coating based on epoxy resin to plastic deformation is low, resulting in cracks in the pavement and its detachment from the stem after repeated cooling and heating in the winter and the summer.

In the patent of Russian Federation №2039070 (1995.07.09) (applicants and inventors: Epifanovsky I.S., Dimitrenko SCI, Y.V. Polezhaev, YU.V. Medvedev, Miraculi DS.) proposed to use glass microspheres as a filler to obtain a flame-retardant coating on a variety of surfaces on the basis of the composition containing siloxane rubber, glass microspheres, the boron nitride. This coating does not have good adhesion (adhesion) with the surface to be coated finish material, as well as a low plasticity and, consequently, high brittleness, which should dramatically reduce the durability of the coating.

From RU 97118225, 1999, known coating made from the composition comprising the polymer as a binder of polyolefin composition (60-99 wt.%) and from 1 to 40 wt.% hollow glass microspheres (inorganic glass), having a density of from 0.05 to 0.6 g/cm3, polyolefin composition as polyolefins includes homopolymers of propylene, ethylene and / or a crystalline copolymer of propylene-ethylene and other copolymers With4-C10alpha-olefins optionally, titanium dioxide, the phenolic stabilizer type, as well as organic phosphonic or postit. The composition used for coating (anti-corrosion, insulation) inner and outer surface of the metal pipe, which is applied by spray welding torch. The coating can provide thermal and corrosion protection for metal surfaces, however, it is well known that polyolefin polymer materials have a very low adhesion to most surfaces, including metal, which ultimately leads to a rapid exfoliation of the surface, in addition, the method of applying such compositions technologically rather simple. That is, it does not have good corrosion protection, and has low adhesion with the substrate.

In U.S. patent No. 4689358 (applicant - Brooklyn Union Gas Company (US), inventors: H. Peter Schorr, Lack J. Fontana, Meyer Steinberg) proposed to use ceramic microspheres or expanded perlite coated with a layer of polystyrene, as filler for cement or mixture of epoxy resins. In this case, the hardened coating has a sufficiently good heat-shielding layer, and it can prevent the heat flammable liquids (flammable liquids) during storage in pre-coated with such coating vessels, which leads to a lower level ve is hatnote explosion or fire on the storage of flammable liquids. However, the use of such coatings is inconvenient from a technological point of view, since it is necessary to prepare a mixture of ceramic spheres with liquid basis directly before coating. In addition, the degree of corrosion protection in this case for the finished concrete surface is insufficient.

The technical objective of the claimed invention is to increase the degree of corrosion and heat-insulating protection to the coated surface, increase adhesion.

The goal of the project is achieved by the fact that anti-corrosion and thermal insulation coating made from a composition including a polymer binder and hollow microspheres caused, at least in the form of one layer, followed by drying it, made of a water-suspension of a composition with a viscosity of 1 to 100 PA·with, as a polymeric binder composition contains a water-based polymer latex composition comprising from 10 to 90 vol.% (co)polymer selected from the group comprising a homopolymer of an acrylate, a copolymer of stirolakrilat, the best choice copolymer, polystyrene, butadiene polymer, a polyurethane polymer, a polymer or copolymer of vinyl acetate or mixtures thereof and from 10 to 90 vol.% a mixture of water and surfactant, as hollow microspheres composition contains a mixture of hollow microspheres with the diversified sizes from 10 to 500 micrometers (μm) and different bulk density of 650 to 50 kg/m 3selected from the group comprising hollow glass microspheres, hollow ceramic microspheres, hollow polymeric microspheres, hollow man-made (ash) microspheres, or a mixture thereof in the following ratio of the components of the water-suspension composition, vol.%:

the above polymer latex composition 5-95

the above hollow microspheres 5-95

Water-based polymer latex composition used as the polymeric binder in the claimed anti-corrosion and insulating coating may additionally contain various white pigments, such as titanium dioxide, zinc oxide, etc., dyes (colored) pigments such as iron oxide pigments, pigments based on chromium oxides, phtalocyanine blue and others;

flame retardant (flame retardant) additives, such as, for example, aluminum trihydrate, ammonium polyphosphate, zinc borate, mica, asbestos, and others;

the rust converters, such as, for example, the Converter PSR-2 on the basis of phosphoric acid, No. 444 on the basis of phosphoric acid, and others;

corrosion inhibitors, such as, for example, sodium nitrite, sodium benzoate, chromate guanidine, tetrachromat zinc, AKOR-1, NG-203 in amounts conventionally used in such similar aqueous dispersions.

As the polymer binder composition used to receive anti-corrosion and insulation coatings according to the invention, contains known as latexes based (co)polymers of acrylate, styrene, vinyl acetate, butadiene-styrene copolymer, polyurethane, polyvinyl chloride (PVC polymer)containing water and a surfactant, such as ethoxylated ALKYLPHENOLS, such as OP-6, OP 7, OP-10, proxenol based on block copolymers of ethylene oxide and propylene, and other traditionally used in water-based systems; and various other additives target, such as white pigments and dyes, corrosion inhibitors, rust converters, flame retardants and other, and also cooked directly on the basis of the latexes of the above or mixtures of polymers when the content of polymer in the composition is from 5 to 95 vol.%.

For example, when receiving anti-corrosion and insulation coatings according to the invention as a polymer binder composition contains a latex polymer systems, as latexes based on copolymers of vinyl acetate with ethylene, methyl methacrylate and methacrylic acid (base paints e-SU-511, e-SU-17), on the basis of polyvinyl acetate dispersion (50%) in the form of paints e-VA-27, e-WA-0112 and others; latex system (paint) on the basis of the best choice copolymer SCS-GP, BS-30, based on acrylic copolymers DMA-GP, and styrene-acrylic company “Dow Chem”, Primal 219N, acrylic is the first MBI-5S, the polyurethane.

Hollow microspheres are one of the most important fillers used in the manufacture of plastics. The spherical shape controlled size and low density make them they are often irreplaceable. An important effect of applying them is to reduce costs of expensive or scarce polymers, as well as a decrease in the density. Traditionally they have a size of from 25 μm to 50 mm and a density of from 100 to 700 kg/m3.

In the claimed invention using mixtures of hollow microspheres (glass, ceramic, polymer, ash), the same or different, but with different sizes in the range from 10 to 500 μm and a variety of bulk density in the range from 50 to 650 kg/m3allows to significantly improve the efficiency of protection of surface treated materials (wood, concrete, plaster, metal from corrosion and thermal insulation.

Such properties of hollow microspheres as low Malopolskie, inertness and ease of dispersion, making them very attractive as fillers.

Hollow microspheres of glass, ceramics, polymers predominantly obtained by introducing a blowing agent into the basic material, the subsequent grinding and heating for foaming of the blowing agent.

So, for example, hollow microspheres obtained by transmission of small particles containing porofor across the high temperature zone; particles melt or soften in the hot zone, and the blowing agent forms a cavity inside the particle, expanding them. Upon cooling of the sphere in the air its walls harden. Either get them by foaming glass (or ceramic) particles in the flame of the burner, etc. as hollow glass microspheres are used, for example, microspheres of the type of the Voice of Babes, type Microballoon; globanet, spherulite. Ceramic microspheres are also by burning natural materials and foaming.

Polymeric hollow microspheres receive as a rule or suspension polymerization of the monomers with the addition of pore-forming (porofor, inert gases, low boiling hydrocarbons), or by physical or chemical foaming ready polymeric regrind particles. As hollow polymeric microspheres of the invention using hollow microspheres, for example of polystyrene, based on phenol-formaldehyde resins, silicone, urea-formaldehyde resins, and others.

The invention

In the present invention proposes a method of manufacturing corrosion-resistant coating having both high heat-shielding properties. As one of the main components of this type of coverage are hollow glass, ceramic, industrial (ash) and polymeric microspheres, Zap Lennie discharged and atmospheric air. The second main component of the coating, in contrast to all of the above patent analogues, are aqueous dispersions of polymer resins, which harden and polymerize after evaporation of the water in the dispersion. Thoroughly mixed with the liquid resin microspheres are excellent anti-corrosion and heat-shielding coating with high adhesion properties. The work of adhesion of the coating to various surfaces, and the degree of permeability of the coating is determined by the type of polymeric binder.

For this type of insulating coatings are applied acrylate, stirolakrilat, polyurethane, best choice, polybutadiene, polystyrene, vinyl acetate, polyvinyl chloride and other water emulsion (latex) of polymer resins, which are immersed and mixed microspheres. The content of the microspheres in the finished composition can be different and vary from 5 to 95 vol.%. The latexes may be used in pure form or blended together in different proportions to achieve different degrees of breathability of the resulting coating and the adhesion of the coating to damage surfaces. For example, when using blends the best choice and acrylate latex (base, in which are placed microspheres) it is possible to obtain coatings with different the second degree breathability - from highly permeable to high barrier against water vapor. A mixture with a high content of best choice latex has high barrier properties against water vapor and containing a large amount of acrylate latex mixture has the properties of good paropronitsaema abilities.

To obtain coatings with the lowest amount of free space between the microspheres and, as a consequence, with high thermal insulation characteristics, it is necessary to use a mixture of hollow microspheres with different radii (from 10 to 500 micrometers) and different bulk densities (from 650 to 50 kg/m3) (Figure 1). You can use microspheres with similar sizes of the radii of the spheres, but in this case, the degree of filling of the space between the spheres is lower (Figure 2).

The importance of the type of polymeric binder used for the microspheres. So in the case of application of coatings for high temperature uses (up to +150° (C) you must apply polyurethane, acrylate, sterility latexes and mixtures thereof. For other types of applications you can use all of the above (for example, the best choice acetate) or other types of water-based latexes such as copolymer, and mixtures thereof. To obtain coatings that can withstand multiple PE epadi temperatures from -70 to 100° C, mixtures are used based latexes with a high degree of plasticity, such as the best choice, butadiene, polyvinyl chloride, copolymer (based on all of the above latexes), or a mixture thereof. Polyurethane, acrylate, sterility latexes and mixtures thereof also have a high resistance to repeated temperature changes, does not lead to cracking in the temperature range from -45 to 150°C. highly Filled ceramic microspheres coatings have a high capacity for reflection and scattering radiation component incident on the surface heat flux. To make the coating more high properties with respect to the reflection and scattering of the incident radiation, including infrared, the composition of the mixture include various white, for example, Tio2, ZnO, and others. The ability of the microspheres to scatter and reflect incident light, including infrared (thermal radiation), is of great importance for this type of coating, because it is able to reflect heat radiation with a high degree of efficiency up to 95% of the incident light stream.

If necessary, the mixture is added to the dispersion and the water-soluble dyes, which give the coverage required by the end user color. In addition, in the liquid composition is water-based mixtures are included, and other components - inhibitors and rust converters, surfactants, stabilizing the suspension, thus preventing the loss of individual components with high density in the sediment or floating of the lungs microspheres, flame retardants (components, preventing the spread of flame in the finished coating, for example trihydrate aluminum), etc.

The mixture may have a different viscosity from 1 to 100 PA·with, however, for better stabilization of the components in the liquid composition is better to use a high viscosity mixture. Methods of applying liquid latex composition may be different, for example it can be applied using spray gun airless spray, brush or roller from one to five layers with thorough drying each layer before applying the next.

Sample preparation

Water-based blend of styrene-acrylic latex was carefully peremesheno with glass microspheres of three types of sizes (average radii of the microspheres 35, 100 and 200 micrometers with facile densities 650, 150, 70 kg/m3in the ratio of 3:6:1, respectively), possibly titanium dioxide, surface-active additives, and rust inhibitor. The volumetric ratio of styrene-acrylic latex to glass microspheres in this case was 1:10. The mixture was deposited on the surface m is a metallic tube of a heat supply, which was filled with hot water with a temperature of pipe surface +115°C. the mixture was applied on the pipe surface using a roller, the thickness of a coating layer was about 0.4 mm after day after applying the first layer (the time required for complete drying of the coating) on the pipe was applied following the coating layer. Thus, it was applied five-layer coating with a total thickness of the finished layer is about 2 mm.

The result after application of the coating with a total thickness of 2 mm, the surface temperature of pipes in a room with an ambient temperature of 20°With, was about +50°and was reduced to +30°C - +40°if the premises weak flow of ambient air. The coating has very good adhesion to the substrate, i.e. adhesion (adhesion 1 point), good physical and mechanical properties:

hardness (pendulum device) 0,5-0,7

elasticity of 1 mm (WD-1)

resistance to shock 50 to

water resistance is good

the light fastness is good

weather resistance - good

The table shows examples of compositions used to obtain anti-corrosion and insulation coatings according to the invention

1. Anti-corrosion and thermal insulation coating made from the composition, comprising a polymeric binder and hollow microspheres and caused at least in one layer on the surface, followed by drying of the coating, characterized in that it is made of a water-suspension of a composition with a viscosity of 1 to 100 PA·with, as a polymeric binder composition contains a water-based polymer latex composition comprising from 10 to 90 vol.% (co)polymer selected from the group comprising a homopolymer of acrylate, styrene-acrylate copolymer, butadiene-styrene copolymer, polystyrene, butadiene polymer, a polyvinyl chloride polymer, a polyurethane polymer, a polymer or copolymer of vinyl acetate or mixtures thereof and from 10 to 90 vol.% a mixture of water and surfactant, as hollow microspheres composition contains a mixture of hollow microspheres with different sizes from 10 to 500 μm and different bulk density of 650 to 50 kg/m3selected from the group comprising hollow glass microspheres, hollow ceramic microspheres, hollow polymeric microspheres, hollow man-made (ash) microspheres, or a mixture thereof in the following ratio of the components of the water-suspension compositions about. %:

Polymer latex composition 5-95

The above hollow microspheres 5-95

2. Corrosion-resistant and heat-insulating covering according to claim 1, characterized in that the water-based latex painted. what Naya polymer composition further comprises a white pigment.

3. Corrosion-resistant and heat-insulating covering according to claim 1 or 2, characterized in that the aqueous dispersion of latex polymer composition further comprises a pigment.

4. Anti-corrosion and thermal insulation coating according to one of claims 1, 2 or 3, characterized in that the aqueous dispersion of latex polymer composition further comprises a flame retardant additive.

5. Anti-corrosion and thermal insulation coating according to one of claims 1, 2, 3 or 4 further comprises a corrosion inhibitor and rust Converter.



 

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