CN109054607B

CN109054607B - Heat insulating material and preparation method thereof

Info

Publication number: CN109054607B
Application number: CN201810703105.1A
Authority: CN
Inventors: 彭代信; 唐波; 宋晓静
Original assignee: Suzhou Yiketai Electronic Material Co ltd
Current assignee: Suzhou Yiketai Electronic Material Co ltd
Priority date: 2018-06-15
Filing date: 2018-06-15
Publication date: 2021-03-19
Anticipated expiration: 2038-06-15
Also published as: CN109054607A

Abstract

The invention discloses a heat insulating material and a preparation method thereof; firstly preparing functional filler, then preparing a functional modification system through organic-inorganic hybrid reaction, and finally obtaining a product with optimal performance by combining a reasonable formula of organic matters with the functional modification system under the condition of limiting the proportion of raw materials. Because a certain amount of silicon-oxygen groups and epoxy groups are introduced into the structure of the product, the obtained product has excellent heat resistance and bonding performance, simple preparation process and low requirement on equipment, is suitable for industrial amplification production, particularly creatively provides the preparation of functional filler, combines the adoption of different organic components, is easier to disperse in the coating, reduces the agglomeration phenomenon, improves the adhesive force of the coating, has excellent performance of the obtained coating, can effectively reduce the temperature of the outer surface and the internal environment of the material, and plays a role in heat insulation.

Description

Heat insulating material and preparation method thereof

Technical Field

The invention relates to a heat insulation material and a preparation method thereof, which can be used in the fields of buildings, devices, containers, external walls and the like.

Background

At present, heat insulating materials are widely applied in the fields of aerospace, construction, chemical engineering and the like, and the existing research focuses mainly on selection of functional materials, such as indium tin oxide, antimony tin oxide, titanium dioxide and the like. The basic principle is to utilize the spectral selectivity of the nano material, but the heat insulation film has the problems that the heat insulation effect is still to be improved and the heat insulation film is still lack of the stability, ultraviolet aging resistance, water resistance and the like.

Disclosure of Invention

The invention provides a heat insulation material and a preparation method thereof, aiming at the current situations of insufficient heat resistance and poor heat insulation effect of the existing heat insulation material.

In order to achieve the purpose of the invention, the technical scheme is as follows:

a heat insulating material and a preparation method thereof are disclosed, the preparation method comprises the following steps:

(1) under the protection of nitrogen, mixing ammonium hexachloroiridate, hydrated nickel nitrate, cobalt nitrate, ethanol and propionic acid; then refluxing and stirring for 110 minutes, and then adding ammonia water and sodium chloride; refluxing and reacting for 10 minutes; then removing the solvent to obtain a solid; carrying out heat treatment on the solid, grinding, soaking in water, and drying to obtain a filler; the heat treatment is sintering at 200 ℃ for 15 minutes, then calcining at 400 ℃ for 15 minutes, and then calcining at 650 ℃ for 5 minutes; mixing a filler, formamidine, hexamethylene diisocyanate, N-methyl pyrrolidone, 2-mercaptopyridine and triphenyl silanol, mechanically stirring for 2 hours, and then carrying out ultrasonic treatment for 3 hours to obtain a functional filler;

(2) mixing a polyvinyl alcohol aqueous solution, iron tetraphenylporphyrin and tert-butyl peroxybenzoate, stirring for 1 hour at 80 ℃, removing water, then adding a dimethyl dimethoxysilane solution, 1, 3, 5-triglycidyl-S-triazine trione and a functional filler, stirring for 50 minutes, then adding glycerol and ethyl orthosilicate, and stirring for 30 minutes to obtain a modified system;

(3) mixing the modified system with hexamethyltriethylenetetramine, trihydrocarbylmonochlorosilane, isopropanol and diglycidyl phthalate, and stirring at 80 ℃ for 1 hour; adding sodium hexametaphosphate, maleic anhydride and cardanol, and stirring at 110 ℃ for 1 hour to obtain a heat insulation system;

(4) coating the surface of a substrate with the heat insulation system, and drying for 8 minutes at 75 ℃; then curing for 5 minutes at 115 ℃ to obtain a heat-insulating material; the base material is concrete, a surface-treated metal plate or a surface-treated plastic plate.

A heat insulation structure and a preparation method thereof are disclosed, the preparation method comprises the following steps:

(4) coating the surface of a substrate with the heat insulation system, and drying for 8 minutes at 75 ℃; then curing for 5 minutes at 115 ℃ to obtain a heat-insulating material; the base material is concrete, a surface-treated metal plate or a surface-treated plastic plate;

(5) and (5) assembling and installing the heat insulation materials to obtain the heat insulation structure.

A heat insulation system and a preparation method thereof are disclosed, the preparation method comprises the following steps:

(3) mixing the modified system with hexamethyltriethylenetetramine, trihydrocarbylmonochlorosilane, isopropanol and diglycidyl phthalate, and stirring at 80 ℃ for 1 hour; and adding sodium hexametaphosphate, maleic anhydride and cardanol, and stirring at 110 ℃ for 1 hour to obtain a heat insulation system.

A thermal insulation system prepared according to the above method for preparing a thermal insulation system; the heat insulating material prepared by the preparation method of the heat insulating material; the heat insulation structure prepared by the preparation method of the heat insulation structure.

The use of the insulation system in the manufacture of the insulation material or insulation structure.

In the technical scheme, the fly ash, the cement, the river sand, the broken stone and the water are mixed and stirred for 30 minutes, then the calcium carbide and the lime are added, and the stirring is continued for 20 minutes to obtain a precursor; curing and solidifying the precursor to obtain concrete, wherein the mass ratio of the fly ash, the cement, the river sand, the broken stone, the calcium carbide and the lime is 11: 100: 26: 22: 10: 15, and the curing and solidifying time is 20 days; the surface-treated metal plate is an anodized aluminum plate; the surface treated plastic panel was a corona treated polypropylene/polyethylene panel.

In the technical scheme, when the base material is concrete, the heat insulation material is assembled and installed by adopting a metal structural member to obtain a heat insulation structure; when the base material is a metal plate with a treated surface, the heat insulation materials are assembled and installed by welding to obtain a heat insulation structure; when the base material is a plastic plate with a surface treated, the heat insulation materials are assembled and installed by adopting structural adhesive bonding, and the heat insulation structure is obtained. The specific combined installation method is the conventional technology, and the heat insulation structure can be a frame.

In the technical scheme, the solvent in the dimethyl dimethoxysilane solution is toluene; removing the solvent by ventilation; the mass concentration of the ammonia water is 22 percent; the particle size of the filler is 0.23-0.28 microns. The surface effect of the nano particles enables the nano particles to have high surface energy, the nano particles are easily combined with organic components in the coating, the compactness of the coating is greatly improved, holes and defects of the coating are greatly reduced, the modified functional filler is more easily dispersed in the coating, the agglomeration phenomenon is reduced, and the adhesion, heat insulation, waterproofness, rheological property and glossiness of the coating are more excellent than those of the prior art.

In the technical scheme, the mass ratio of the ammonium hexachloroiridate to the hydrated nickel nitrate to the cobalt nitrate to the ethanol to the propionic acid to the ammonia water to the sodium chloride is 100: 73: 42: 220: 32: 29: 15. Propionic acid and ammonia water can provide good mixing conditions, so that the metal elements which play a role are well matched, sodium chloride enables the heat of solids to be uniformly dispersed during sintering, more importantly, a nano-scale product can be obtained, the surface of the nano-particle presents a cavity, the adhesive interface action area and the interface action force of organic matters and fillers are improved, and the thermal stability and the water absorption rate of the coating of the embodiment are shown. The functional filler can obtain higher reflectivity at low cost, and can greatly reduce the cost of the reflective heat-insulating coating.

In the technical scheme, the mass ratio of the filler, the formamidine, the hexamethylene diisocyanate, the N-methylpyrrolidone, the 2-mercaptopyridine and the triphenyl silanol is 100: 6: 82: 33: 32: 59. The nano particles modified by hexamethylene diisocyanate, N-methyl pyrrolidone, 2-mercaptopyridine and triphenyl silanol are used as functional fillers, organic matter units react on the surfaces of the nano particles to form a layer of organic matter film, the organic matter film can react with other organic components of a heat insulation system, and the nano particles can be prevented from contacting with each other, so that the interface binding force of the nano particles can be improved, and the internal defects of the material can be reduced.

In the technical scheme, the mass ratio of the polyvinyl alcohol, the iron tetraphenylporphyrin, the tert-butyl peroxybenzoate, the dimethyl dimethoxysilane solution, the 1, 3, 5-triglycidyl-S-triazine trione, the functional filler, the glycerol and the ethyl orthosilicate is 100: 8: 35: 70: 55: 22.

The cured coating contains stable benzene rings, silicon, phosphorus and the like, and a paint film has good adhesion to a base material, small structural pores, compact structure, excellent heat-insulating property and a protective effect on a matrix.

In the technical scheme, the mass ratio of the modification system, hexamethyl triethylene tetramine, trialkyl monochlorosilane, isopropanol, diglycidyl phthalate, sodium hexametaphosphate, maleic anhydride and cardanol is 100: 55: 28: 80: 12: 9: 38: 16.

The invention avoids the use of conventional resins such as epoxy resin, amino resin, phenolic resin, acrylic resin and the like, adopts a plurality of groups of organic compounds through proportioning limitation and preparation process selection, obtains a coating with the advantages of lower voc content, no pungent smell and the like, and can also show the advantages which the common resin does not have after curing to form a film, such as good gloss, water resistance, adhesiveness and the like.

In the technical scheme, the thickness of the heat insulation material is 0.1-0.15 mm. The use of the filler is an innovative point of the invention, and from the application effect of the implementation of the invention, the iridium nickel cobalt can be matched with the iridium nickel cobalt to enhance the heat insulation property of the coating material and improve the strength of the coating, so that the service life of the coating can be prolonged.

The organic compound such as hexamethylene diisocyanate, tert-butyl peroxybenzoate, 2-mercaptopyridine, maleic anhydride, cardanol, formamidine and the like not only has the effect of dispersing aggregates by using a conventional coupling agent, but also has the advantages of high reaction efficiency, good dispersion effect, stable existence among particles, guarantee of filler dispersion, and good reaction with other components such as hexamethyltriethylenetetramine, diglycidyl phthalate, triphenyl silanol, trihydrocarbyl monochlorosilane and the like, can improve the problem of shrinkage cavity of a coating material caused by surface tension, can remarkably reduce the viscosity of a system, and finally participate in curing and film forming in the reaction, and has small influence on the physical properties of the system.

The paint has high heat insulation performance and excellent oil-resistant aging performance, and the film forming substance integrates the advantages of high adhesive force, high strength and low shrinkage of diglycidyl phthalate, 1, 3, 5-triglycidyl-S-triazine trione and hexamethylene diisocyanate, the excellent flexibility of polyvinyl alcohol, N-methyl pyrrolidone and 2-mercaptopyridine, the excellent flexibility of triphenyl silanol, hexamethyl triethylene tetramine, trihydrocarbyl monochlorosilane oil-resistant aging performance, sodium hexametaphosphate and cardanol film forming performance, and can play a role in curing due to the reaction groups contained in maleic anhydride and ethyl orthosilicate; in short, the resin film has a high reflectance to sunlight and excellent heat insulating properties.

The thickness of the existing heat insulation coating material is generally 300-500 mu m, while the coating on the surface of the heat insulation material is a thin material, the thickness range of the coating is 0.1-0.15 mm, a compact thin film can be formed on the surface of a base material, and the thin film can reflect heat, so that the heat insulation effect is exerted, and meanwhile, the heat insulation coating material has the advantages of low cost, simple formula, convenience in construction, oil resistance, aging resistance, waterproof performance and the like.

Detailed Description

The technical solution of the present invention is further illustrated by the following examples.

The compounds are used in combination, so that the surface drying time and the actual drying time of the product are very short, the adhesive force is high, and the water absorption rate is low; the coating is based on functional fillers and organic components, has good weather resistance, high heat insulation and refractive index, high reflection performance to solar radiant heat and low heat conductivity to heat conduction, is a coating with reflection and barrier dual heat insulation performance, and can effectively reduce the outer surface temperature and the internal environment temperature of a matrix; the coating of the invention is stable to oxygen, hydrogen sulfide, disulfide trioxide and ammonia in the atmosphere, has good heat resistance, reduces the heat conductivity coefficient of the coating by the functional filler, improves the washing resistance and the self-cleaning property of the coating surface, can also increase the stability of the coating system, can improve the wettability of the filler by adopting the functional components, prevents the floating color and the floating color of the coating, has better foam inhibition and leveling property when the coating is dispersed, can prevent the flocculation of the coating, and is suitable for the surfaces of various substrates.

Example one

Mixing and stirring fly ash, cement, river sand, broken stone and water for 30 minutes, adding calcium carbide and lime, and continuously stirring for 20 minutes to obtain a precursor; curing and solidifying the precursor to obtain concrete; the mass ratio of the fly ash, the cement, the river sand, the broken stone, the calcium carbide and the lime is 11: 100: 26: 22: 10: 15, the adding amount of water is added according to the actual requirement, and the conventional technology is adopted; the curing time is 20 days.

Carrying out conventional corona surface treatment on a plastic plate (polypropylene/polyethylene) to obtain a surface-treated plastic plate; the aluminum plate is subjected to conventional anodic oxidation surface treatment to obtain a surface-treated metal plate, a paint film in the scratch range of a round rolling line is complete and does not fall off, and the adhesive force is grade 1.

Combining a concrete heat-insulating material and a metal structural member through bolts, and mounting a plurality of the concrete heat-insulating material and the metal structural member in a combined manner to obtain a heat-insulating structure; the metal structural parts and the concrete combination and installation mode are the prior art, for example, the triangular iron is utilized to be combined and overlapped to form a frame building structure.

The heat insulating material of the plastic plate is combined by conventional structural adhesive to obtain a heat insulating structure which is a frame and used for outdoor decoration.

And welding and assembling the metal plate heat insulation materials to obtain a heat insulation structure, welding the heat insulation structure at 179 ℃ by using M51 and M51-F welding wires, wherein the metal structure is a frame and is used for a curtain wall.

In the first comparative example, on the basis of the first example, the filler is replaced by the nano silica, the rest is unchanged, and the adhesion is grade 1.

Comparative example II on the basis of example I, formamidine, hexamethylene diisocyanate, N-methylpyrrolidone, 2-mercaptopyridine and triphenylsilanol are replaced by KH550 with the mass of 1.5% of that of the filler, and the balance is unchanged, so that the adhesion is grade 2.

Comparative example III, on the basis of example I, the dimethyl dimethoxy silane solution and the 1, 3, 5-triglycidyl-S-triazinetrione are not added, and the rest is unchanged, and the adhesion is grade 1.

Comparative example four, on the basis of example one, do not add hexamethyltriethylenetetramine, three hydrocarbyl monochlorosilane, the others are unchanged, the adhesion is grade 1.

In a fifth comparative example, on the basis of the first example, sodium hexametaphosphate, maleic anhydride and cardanol were not added, and the balance was unchanged, the adhesion was grade 2, and the coating was slightly broken.

And (3) detecting the performance of the coating material, wherein the thickness of the obtained coating on the surface of the heat-insulating material is 0.12-0.13 mm, and the cured coating is flat and free of defects such as bubbles and cracks.

The aluminum plate heat insulating material with the length and width of 40mm multiplied by 40mm is taken. The solar reflectance of the coating was then measured using an ultraviolet spectrophotometer. The solar reflectance of the thermal insulation material of the example reaches 95% in the visible and near infrared bands where the main energy of sunlight is concentrated, and 69%, 81%, 85%, 75%, 88% in the comparative examples, respectively, which shows that the coating of the present invention has high reflectance to sunlight.

The thermal insulation material of the plastic plate is made into a box body with the square of 50cm, the exterior of the box body is wrapped and sealed by tinfoil, a testing light source is a 500w iodine-tungsten lamp, the distance from the testing side surface is 50cm, a temperature measuring point is respectively arranged at the center of the surface of the testing side surface and the center of the interior of the box body, then the temperature rise conditions of the internal temperature measuring points are compared, and the testing time is 1 h. Through tests, the internal temperature of the coating is increased by 15.3 ℃ without brushing, the internal temperature of the heat insulation material of the embodiment is increased by 6.1 ℃, and the internal temperatures of the comparative examples are respectively increased by 13.2 ℃, 11.1 ℃, 11.9 ℃, 10.5 ℃ and 8.8 ℃, which shows that the heat insulation material of the invention has excellent heat insulation and temperature reduction effects.

The water absorption rates in boiling for 120 hours of the coatings of example one and comparative examples one to five were 1.11%, 1.56%, 1.29%, 2.28%, 2.51%, 2.72%, respectively.

Under the test of resisting wet heat for 2000 hours, the first and the second comparative examples have no peeling and no foaming, the first, the fourth and the fifth comparative examples have slight foaming, and the third comparative example has severe foaming.

The scrub resistance test is carried out according to GB/T9266-2009, the scrubbing resistance times of the coating of the heat-insulating material in the first example are more than 4000, and the scrubbing resistance times of the coating of the heat-insulating material in the first to fifth examples are 3000, 3300, 2000, 3800 and 3600 respectively, which shows that the heat-insulating material has excellent scrubbing resistance.

The mixture is calcined at 250 ℃ for 5 minutes, and the carbonization phenomenon does not appear in the first example and the first comparative example, the obvious carbonization phenomenon appears in the third comparative example and the second comparative example, and the slight carbonization phenomenon appears in the fourth comparative example and the fifth comparative example.

Claims

1. The preparation method of the heat insulation material is characterized by comprising the following steps of:

(4) coating the surface of a substrate with the heat insulation system, and drying for 8 minutes at 75 ℃; then curing for 5 minutes at 115 ℃ to obtain a heat-insulating material; the base material is concrete.

2. The preparation method according to claim 1, wherein the mass ratio of the ammonium hexachloroiridate, the hydrated nickel nitrate, the cobalt nitrate, the ethanol, the propionic acid, the ammonia water and the sodium chloride is 100: 73: 42: 220: 32: 29: 15; the mass ratio of the filler, the formamidine, the hexamethylene diisocyanate, the N-methyl pyrrolidone, the 2-mercaptopyridine and the triphenyl silanol is 100: 6: 82: 33: 32: 59; the mass ratio of the polyvinyl alcohol, the iron tetraphenylporphyrin, the tert-butyl peroxybenzoate, the dimethyl dimethoxy silane solution, the 1, 3, 5-triglycidyl-S-triazine trione, the functional filler, the glycerol and the ethyl orthosilicate is 100: 8: 35: 70: 55: 22; the mass ratio of the modification system, hexamethyltriethylenetetramine, trihydrocarbyl monochlorosilane, isopropanol, diglycidyl phthalate, sodium hexametaphosphate, maleic anhydride and cardanol is 100: 55: 28: 80: 12: 9: 38: 16.

3. The method according to claim 1, wherein the solvent is removed by aeration; the mass concentration of the ammonia water is 22 percent; the particle size of the filler is 0.23-0.28 microns; in the dimethyl dimethoxy silane solution, the solvent is toluene.

4. The preparation method according to claim 1, characterized in that fly ash, cement, river sand, broken stone and water are mixed and stirred for 30 minutes, then calcium carbide and lime are added, and stirring is continued for 20 minutes to obtain a precursor; curing and curing the precursor to obtain the concrete.