Organic-inorganic composite heat insulation medium and preparation method thereof

Abstract

The present invention discloses an organic-inorganic composite heat insulation medium, which is characterized in that its structure is (M x -R n )WO y nanoparticles with a particle size of 10-50 nm, where M represents a doped metal element, R is an organic complex group, 0.3 ≤ x ≤ 0.7, 2 < y < 4, n is the degree of polymerization of the organic group, and n ≥ 10. In addition, the present invention also discloses a preparation method of the heat insulation medium. The organic-inorganic composite heat insulation medium of the present invention has both high heat insulation and durability, and high transparency and high clarity, and can be applied to various products such as films, slurries, and coatings to achieve high-performance heat insulation functions.

Description

Technical Field

[0001] The present invention relates to an organic-inorganic composite heat insulation medium. In addition, the present invention also relates to a preparation method of the foregoing organic-inorganic composite heat insulation medium. Background Art

[0002] The efficient utilization of energy is an important topic in current development. With the trend of global warming, high-temperature weather has become common. For this reason, air-conditioning facilities are often used for temperature regulation in spaces such as buildings and cars, which often consume a large amount of energy. The energy consumed by cooling and temperature control equipment each year accounts for about 20% of the total energy consumption. Functional materials such as heat insulation media have emerged as the times require. In summer, the heat insulation medium absorbs infrared light and ultraviolet light, converts it into heat energy or reflects it, and transfers heat to the air in the form of heat conduction and heat convection. 50% of the heat is transferred to the outdoor air, and the rest is transferred to the interior, reducing the internal heat by about half, thereby reducing the energy consumption of air conditioners and the like by about half, achieving a good energy-saving effect. In winter, the indoor heat is transferred to the outdoor in the form of thermal radiation, and the heat insulation medium can also absorb or reflect the infrared light back into the room. About half of the heat returns to the room in the form of heat convection, reducing heat loss and also achieving an energy-saving effect.

[0003] Currently, the development of heat insulation media mostly adopts a single inorganic or organic structure. International Patent CN108884375A discloses a series of infrared absorption materials, including one or more transition metals and their ligands (including one or more elements of B, C, N, O, F, Al, Si, P, S, Cl, Se, Te), which can be applied to thermoplastic resins to prepare infrared absorption transparent substrates. International Patent CN108779381A discloses a near-infrared ray shielding ultrafine particle dispersion, which realizes excellent near-infrared ray shielding property and blue haze suppression effect through composite tungsten oxide M X W Y O Z ultrafine particles. International Patent CN1742214A discloses a near-infrared absorption compound, based on a diphenyl-p-phenylenediamine salt derivative structure, which does not contain harmful substances such as antimony and arsenic, realizes the infrared absorption function, and has excellent heat resistance. These structures all have good infrared absorption characteristics.

[0004] Based on relevant research, through further design and construction, the advantages of organic and inorganic structures can be complementary, and a nano heat insulation medium material with outstanding performance can be prepared. Summary of the Invention

[0005] Aiming at the above-mentioned deficiencies of the prior art, according to the embodiments of the present invention, it is desired to provide an organic-inorganic composite heat insulation medium with simple preparation, good heat resistance, environmental protection and high heat insulation performance, and to propose a preparation method of the heat insulation medium.

[0006] According to an embodiment, an organic-inorganic composite heat insulation medium provided by the present invention has a structure of (M x -R n )WO y nanoparticles with a particle size of 10 - 50 nm, where M represents a doped metal element, R is an organic complex group, 0.3 ≤ x ≤ 0.7, 2 < y < 4, and n is the degree of polymerization of the organic group, n ≥ 10.

[0007] According to one embodiment, in the organic-inorganic composite heat insulation medium of the present invention, the doped metal element is selected from alkali metals, alkaline earth metals, transition metals, and rare earth metals.

[0008] According to one embodiment, in the organic-inorganic composite heat insulation medium of the present invention, the organic complex group R is selected from pyrrole and its derivatives, aniline and its derivatives, and thiophene and its derivatives;

[0009] According to an embodiment, a preparation method of an organic-inorganic composite heat insulation medium provided by the present invention includes the following steps:

[0010] (1) Take 1 part by mass of tungstate and disperse it in a water / ethanol (1 / 1, v / v) system to obtain a solution with a preparation concentration of 0.05 - 0.5 mol / L. Add 0.05 - 0.5 part by mass of a dilute acid solution with a concentration of 0.05 - 0.1 mol / L, ultrasonicate for 10 - 30 min, and carry out an aging reaction for 12 - 24 h.

[0011] (2) After the product is filtered and washed with water, it is successively dispersed in 5 - 10 parts by mass of deionized water together with 0.1 - 0.5 part by mass of metal salt. Add 0.5 - 3 parts by mass of polyol, stir for 0.5 - 2 h, transfer to a pressure reactor, control the pressure at 1 - 5 MPa, control the temperature at 100 - 150 °C, and react for 12 - 24 h.

[0012] (3) Filter and wash the product, disperse it in 5 - 10 parts by mass of solvent, add 0.05 - 0.2 part by mass of active monomer, adjust the pH to 2 - 5 with hydrochloric acid, and carry out a pre-reaction for 1 - 3 h. Add 0.01 - 0.1 part by mass of oxidant and react at 50 - 80 °C for 2 - 5 h.

[0013] (4) After the obtained product is filtered, it is washed with ethanol, vacuum dried for 24 h, and placed in a tube furnace under a nitrogen atmosphere for treatment at 200 - 400 °C for 1 - 5 h to obtain a stable organic-inorganic composite heat insulation medium.

[0014] According to one embodiment, in step (1) of the preparation method of the organic-inorganic composite heat insulation medium of the present invention, the tungstate is selected from sodium tungstate, potassium tungstate, and ammonium tungstate.

[0015] According to one embodiment, in step (1) of the preparation method of the aforementioned organic-inorganic composite heat insulation medium of the present invention, the dilute acid solution is selected from dilute hydrochloric acid and dilute nitric acid.

[0016] According to one embodiment, in step (2) of the preparation method of the aforementioned organic-inorganic composite heat insulation medium of the present invention, the metal salt is selected from soluble chlorides, sulfates and nitrates doped with metal elements.

[0017] According to one embodiment, in step (2) of the preparation method of the aforementioned organic-inorganic composite heat insulation medium of the present invention, the polyol is selected from ethylene glycol, 1,3-propanediol and glycerol.

[0018] According to one embodiment, in step (3) of the preparation method of the aforementioned organic-inorganic composite heat insulation medium of the present invention, the active monomer is selected from pyrrole and its derivatives, aniline and its derivatives, and thiophene and its derivatives.

[0019] According to one embodiment, in step (3) of the preparation method of the aforementioned organic-inorganic composite heat insulation medium of the present invention, the oxidant is selected from ferric chloride and potassium chlorate.

[0020] Compared with the prior art, the organic-inorganic composite nano heat insulation medium of the present invention enables electrons to have stronger mobility in nanoparticles through the conjugation of macromolecular organic structures and inorganic compounds, enhancing the infrared absorption effect and thus achieving a more efficient heat insulation effect. At the same time, through the cross-linking heat treatment of the heat insulation medium, a tight connection structure of organic-organic and organic-inorganic is obtained, further ensuring the stability and weather resistance of the heat insulation medium. On the other hand, due to the nano-scale of the heat insulation medium, its absorption activity will be further enhanced and the transparency of the product will be maintained. Therefore, the organic-inorganic composite nano heat insulation medium of the present invention will have the following outstanding characteristics: Products prepared with this heat insulation medium, such as coatings, slurries, and films, have strong infrared absorption ability, that is, high heat insulation; at the same time, the products can have good weather resistance and stability; on the other hand, due to the small nano-scale of the heat insulation medium, the products can maintain high transparency and high clarity, ensuring the product quality and functional requirements. In addition, the present invention also has the characteristics of a general and simple preparation method, good environmental protection, and low cost. Brief Description of the Drawings

[0021] Figure 1 It is a TEM image of the organic-inorganic composite nano heat insulation medium obtained in Example 1. Detailed Embodiments

[0022] The present invention will be further described below in conjunction with specific embodiments. These embodiments should be understood as being only for the purpose of illustrating the present invention and not for limiting the scope of protection of the present invention. After reading the content recorded in the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent changes and modifications also fall within the scope defined by the claims of the present invention.

[0023] In the following embodiments of the present invention, the raw materials used are all commercially available products unless otherwise specified.

[0024] Example 1

[0025] (1) Take 100 g of sodium tungstate and disperse it in a 3 L water / ethanol system with an equal volume ratio. Add 16 ml of 0.1 mol / L dilute hydrochloric acid, ultrasonicate for 30 min, and age overnight for 12 h.

[0026] (2) Filter and wash the above product, and disperse it with 25 g of yttrium nitrate in 1 L of deionized water successively. Add 67 g of ethylene glycol, stir for 1 h, transfer to a pressure reactor, control the pressure at 2 MPa, control the temperature at 120 °C, and react for 24 h.

[0027] (3) Filter and wash the above product, disperse it in 800 ml of water, add 20 g of pyrrole, adjust the pH to 3 with hydrochloric acid, and pre-react for 1 h. Add 8 g of ferric chloride and react at 75 °C for 3 h.

[0028] (4) After filtering the obtained product, wash it with ethanol, vacuum dry it for 24 h, place it in a tube furnace under a nitrogen atmosphere and treat it at 220 °C for 3 h to obtain a stable organic-inorganic composite thermal insulation medium. Its morphology is as Figure 1 shown, being a nanoparticle structure of about 30 nm.

[0029] Example 2

[0030] (1) Take 110 g of potassium tungstate and disperse it in a 3 L water / ethanol system with an equal volume ratio. Add 18 ml of 0.1 mol / L dilute hydrochloric acid, ultrasonicate for 30 min, and age overnight for 12 h.

[0031] (2) Filter and wash the above product, and disperse it with 14 g of nickel chloride in 800 ml of deionized water successively. Add 58 g of 1,3-propanediol, stir for 1 h, transfer to a pressure reactor, control the pressure at 1.5 MPa, control the temperature at 110 °C, and react for 24 h.

[0032] (3) Filter and wash the above product, disperse it in 800 ml of water, add 22 g of aniline, adjust the pH to 2.5 with hydrochloric acid, and pre-react for 1 h. Add 10 g of potassium chlorate and react at 70 °C for 4 h.

[0033] (4) After filtering the obtained product, it was washed with ethanol and dried in vacuum for 24 h. Then it was placed in a tubular furnace under a nitrogen atmosphere and treated at 220 °C for 2 h to obtain a stable organic-inorganic composite heat insulation medium.

[0034] Example 3

[0035] (1) 95 g of ammonium tungstate was dispersed in a 3 L water / ethanol system with an equal volume ratio, 15 ml of 0.1 mol / L dilute hydrochloric acid was added, and it was ultrasonicated for 30 min and aged overnight for 12 h.

[0036] (2) The above product was filtered and washed with water, and then dispersed in 1 L of deionized water successively with 28 g of cerium nitrate. 70 g of 1,3-propanediol was added, and it was stirred for 1 h. Then it was transferred to a pressure reactor, the pressure was controlled at 1.5 MPa, the temperature was controlled at 130 °C, and the reaction was carried out for 24 h.

[0037] (3) The above product was filtered and washed with water, dispersed in 800 ml of water, 22 g of pyrrole was added, the pH was adjusted to 3 with hydrochloric acid, and the pre-reaction was carried out for 1 h. 9 g of ferric chloride was added, and the reaction was carried out at 70 °C for 4 h.

[0038] (4) After filtering the obtained product, it was washed with ethanol and dried in vacuum for 24 h. Then it was placed in a tubular furnace under a nitrogen atmosphere and treated at 280 °C for 1 h to obtain a stable organic-inorganic composite heat insulation medium.

[0039] Example 4

[0040] (1) 100 g of sodium tungstate was dispersed in a 3 L water / ethanol system with an equal volume ratio, 17 ml of 0.1 mol / L dilute hydrochloric acid was added, and it was ultrasonicated for 30 min and aged overnight for 12 h.

[0041] (2) The above product was filtered and washed with water, and then dispersed in 800 ml of deionized water successively with 27 g of molybdenum nitrate. 72 g of ethylene glycol was added, and it was stirred for 1 h. Then it was transferred to a pressure reactor, the pressure was controlled at 2 MPa, the temperature was controlled at 120 °C, and the reaction was carried out for 24 h.

[0042] (3) The above product was filtered and washed with water, dispersed in 800 ml of water, 23 g of aniline was added, the pH was adjusted to 3 with hydrochloric acid, and the pre-reaction was carried out for 1 h. 9 g of potassium chlorate was added, and the reaction was carried out at 75 °C for 4 h.

[0043] (4) After filtering the obtained product, it was washed with ethanol and dried in vacuum for 24 h. Then it was placed in a tubular furnace under a nitrogen atmosphere and treated at 260 °C for 2 h to obtain a stable organic-inorganic composite heat insulation medium.

[0044] Example 5

[0045] (1) Disperse 110 g of potassium tungstate in a 3 L water / ethanol system with equal volume ratio, add 20 ml of 0.1 mol / L dilute hydrochloric acid, sonicate for 30 min, and age overnight for 12 h.

[0046] (2) Filter and wash the above product, and disperse it and 17 g of copper chloride in 800 ml of deionized water successively. Add 74 g of glycerol, stir for 1 h, transfer to a pressure reactor, control the pressure at 2 MPa, control the temperature at 120 °C, and react for 24 h.

[0047] (3) Filter and wash the above product, disperse it in 800 ml of water, add 22 g of thiophene, adjust the pH to 2 with hydrochloric acid, and pre-react for 1 h. Add 10 g of ferric chloride and react at 75 °C for 3 h.

[0048] (4) Filter the obtained product, wash it with ethanol, dry it in vacuum for 24 h, place it in a tubular furnace under a nitrogen atmosphere and treat it at 230 °C for 2 h to obtain a stable organic-inorganic composite thermal insulation medium.

[0049] Example 6

[0050] (1) Disperse 110 g of sodium tungstate in a 3 L water / ethanol system with equal volume ratio, add 21 ml of 0.1 mol / L dilute hydrochloric acid, sonicate for 30 min, and age overnight for 12 h.

[0051] (2) Filter and wash the above product, and disperse it and 30 g of zinc nitrate in 800 ml of deionized water successively. Add 62 g of 1,3-propanediol, stir for 1 h, transfer to a pressure reactor, control the pressure at 1.5 MPa, control the temperature at 120 °C, and react for 24 h.

[0052] (3) Filter and wash the above product, disperse it in 800 ml of water, add 22 g of pyrrole, adjust the pH to 2.5 with hydrochloric acid, and pre-react for 1 h. Add 9 g of potassium chlorate and react at 70 °C for 4 h.

[0053] (4) Filter the obtained product, wash it with ethanol, dry it in vacuum for 24 h, place it in a tubular furnace under a nitrogen atmosphere and treat it at 230 °C for 2 h to obtain a stable organic-inorganic composite thermal insulation medium.

[0054] Example 7

[0055] (1) Disperse 110 g of potassium tungstate in a 3 L water / ethanol system with equal volume ratio, add 20 ml of 0.1 mol / L dilute hydrochloric acid, sonicate for 30 min, and age overnight for 12 h.

[0056] (2) Filter and wash the above product, and disperse it and 32 g of lanthanum nitrate in 800 ml of deionized water successively. Add 65 g of ethylene glycol, stir for 1 h, transfer to a pressure reactor, control the pressure at 2 MPa, control the temperature at 120 °C, and react for 24 h.

[0057] (3) Filter the above product and wash it with water. Disperse it in 800 ml of water, add 22 g of aniline, adjust the pH to 2.5 with hydrochloric acid, and pre-react for 1 h. Add 11 g of ferric chloride and react at 75 °C for 4 h.

[0058] (4) After filtering the obtained product, wash it with ethanol, dry it in vacuum for 24 h, and place it in a tube furnace at 260 °C for 2 h under a nitrogen atmosphere to obtain a stable organic-inorganic composite thermal insulation medium.

[0059] Test Example

[0060] (1) Disperse the organic-inorganic composite thermal insulation medium prepared in Examples 1-7 in ethyl acetate, and control the content to be 20%;

[0061] (2) Obtain a mixture by mixing acrylic resin (solid content 40%), ethyl acetate, and the organic-inorganic composite thermal insulation medium in a ratio of 4:4:2;

[0062] (3) Uniformly coat the mixture on the surface of the PET film, and control the coating thickness to be about 10 microns;

[0063] (4) Immediately cover a layer of PET film above the thermal insulation coating to obtain a three-layer composite film;

[0064] (4) Place the above film in an 80 °C oven, dry it for 5 minutes, and cool it for standby;

[0065] (5) Measure the transmittance of this composite film in the visible light and infrared bands through a spectrophotometer and a light transmittance tester. Select two typical wavelength points of 950 nm and 1400 nm in the infrared band to measure the transmittance, which is the thermal insulation rate; measure the haze through a haze meter to characterize its clarity.

[0066] The test results are shown in Table 1. It can be seen from Table 1 that each example has good visible light transmittance, infrared band blocking rate, and clarity. This indicates that the organic-inorganic composite thermal insulation medium prepared in Examples 1-7 has good transparency, heat insulation, and clarity, and has broad application prospects in fields such as films, slurries, and coatings.

[0067] Table 1. Infrared blocking rate of Examples 1-7

[0068]

Claims

1. An organic-inorganic composite heat insulation medium, characterized in that, Its structure is (M x -R n )WO y nanoparticles with a particle size of 10 - 50 nm, where M represents a doped metal element, R is an organic complex group, 0.3 ≤ x ≤ 0.7, 2 < y < 4, n is the degree of polymerization of the organic group, n ≥ 10; the doped metal element is selected from alkali metals, alkaline earth metals, transition metals and rare earth metals; R is selected from pyrrole and its derivatives, aniline and its derivatives, and thiophene and its derivatives.

2. The preparation method of the organic-inorganic composite heat insulation medium according to claim 1, characterized in that, It includes the following steps: (1) Take 1 part by mass of tungstate and disperse it in a water / ethanol (1 / 1, v / v) system to obtain a solution with a concentration of 0.05 - 0.5 mol / L. Add 0.05 - 0.5 part by mass of a dilute acid solution with a concentration of 0.05 - 0.1 mol / L, ultrasonic for 10 - 30 min, and age the reaction for 12 - 24 h; (2) The product obtained in step (1) is filtered, washed with water, and then dispersed in 5 - 10 parts by mass of deionized water successively with 0.1 - 0.5 part by mass of metal salt. Add 0.5 - 3 parts by mass of polyol, stir for 0.5 - 2 h, transfer to a pressure reactor, control the pressure at 1 - 5 MPa, control the temperature at 100 - 150 °C, and react for 12 - 24 h; (3) Filter and wash the product obtained in step (2), disperse it in 5 - 10 parts by mass of solvent, add 0.05 - 0.2 part by mass of active monomer, adjust the pH to 2 - 5 with hydrochloric acid, pre - react for 1 - 3 h, add 0.01 - 0.1 part by mass of oxidant, and react at 50 - 80 °C for 2 - 5 h; (4) Filter the product obtained in step (3), wash it with ethanol, vacuum dry for 24 h, place it in a tubular furnace under a nitrogen atmosphere and treat it at 200 - 400 °C for 1 - 5 h to obtain a stable organic - inorganic composite thermal insulation medium.

3. The preparation method of the organic-inorganic composite heat insulation medium according to claim 2, characterized in that, In step (1), the tungstate is selected from sodium tungstate, potassium tungstate, and ammonium tungstate.

4. The preparation method of the organic-inorganic composite heat insulation medium according to claim 2, wherein, In step (1), the dilute acid solution is selected from dilute hydrochloric acid and dilute nitric acid.

5. The preparation method of the organic-inorganic composite heat insulation medium according to claim 2, characterized in that, In step (2), the metal salt is selected from soluble chlorides, sulfates, and nitrates doped with metal elements.

6. The preparation method of the organic-inorganic composite heat insulation medium according to claim 2, characterized in that, In step (2), the polyol is selected from ethylene glycol, 1,3 - propanediol, and glycerol.

7. The preparation method of the organic-inorganic composite heat insulation medium according to claim 2, characterized in that, In step (3), the active monomer is selected from pyrrole and its derivatives, aniline and its derivatives, and thiophene and its derivatives.

8. The preparation method of the organic-inorganic composite heat insulation medium according to claim 2, characterized in that, In step (3), the oxidant is selected from ferric chloride and potassium chlorate.

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