A glass material resistant to temperature change and its preparation method

Abstract

The present invention discloses a temperature-resistant glass material and a preparation method thereof, relating to the field of glass. When preparing the temperature-resistant glass material of the present invention, whisker silicon is soaked in an aluminum hydroxide solution, and then heated, mixed, and annealed with nano-silica, lithium oxide, sodium carbonate, and titanium dioxide to obtain glass; alumina is successively reacted with 3-aminopropyltrimethoxysilane, 4-bromo-2-hydroxybenzaldehyde, and 4-aminopyridine to obtain functionalized alumina; a polyaspartic acid ester resin, a hexamethylene diisocyanate-based polyisocyanate trimer, a functional monomer, and a capping agent are reacted to obtain a modified polyurea; the modified polyurea is mixed with the functionalized alumina to obtain a coating material, which is sprayed on the surface of the glass and dried to obtain the temperature-resistant glass material. The temperature-resistant glass material prepared by the present invention has the abilities of anti-fouling, heat conduction, impact resistance, coating self-repair, and aging resistance.

Description

Technical Field

[0001] The present invention relates to the field of glass, and specifically to a temperature-resistant glass material and a preparation method thereof. Background Art

[0002] Since the appearance of glass, it has experienced thousands of years of development. From the colored glaze in ancient China, to the mosaics in Rome, and then to the glass manufacturing industry during the Industrial Revolution, with the progress of technology, the application fields of glass have gradually expanded, covering various aspects such as daily utensils, architectural decoration, glass fiber, electronic information, and biological materials. Among them, in the field of architectural decoration alone, it can be classified into flat glass, decorative glass, safety glass, and energy-saving glass according to different functions.

[0003] With the development of social economy and the continuous improvement of people's living standards, the requirements for the safety performance of glass in buildings are also getting higher and higher. Safety glass refers to glass that can resist severe vibration or impact without breaking, or even if it breaks, it is not easy to hurt people. It is widely used in automobiles, airplanes, and building doors and windows, etc. However, with long-term exposure to sunlight and wind and rain, the glass will generate dirt, thus affecting the visual effect. Therefore, this article introduces a temperature-resistant glass material with anti-fouling ability. Summary of the Invention

[0004] The purpose of the present invention is to provide a temperature-resistant glass material and a preparation method thereof to solve the problems existing in the prior art.

[0005] A temperature-resistant glass material, wherein the temperature-resistant glass material is prepared by mixing modified polyurea and functionalized alumina to obtain a coating material, spraying it on the glass surface, and drying.

[0006] The functionalized alumina is prepared by reacting alumina with 3-aminopropyltrimethoxysilane, 4-bromo-2-hydroxybenzaldehyde, and 4-aminopyridine in sequence.

[0007] The glass is prepared by soaking whisker silicon in an aluminum hydroxide solution, and then heating, mixing, and annealing it with nano-silica, lithium oxide, sodium carbonate, and titanium dioxide.

[0008] The modified polyurea is prepared by reacting polyaspartic acid ester resin F420, polyaspartic acid ester resin F524, hexamethylene diisocyanate-based polyisocyanate trimer, functionalized monomer, and capping agent.

[0009] The functionalized monomer is prepared by reacting 2,2'-bis(trifluoromethyl)diaminobiphenyl and diethyl maleate.

[0010] The capping agent is prepared by reacting 4',4”(5”)-diaminodibenzo-15-crown-5 and diethyl maleate.

[0011] A preparation method of a glass material resistant to temperature change, the preparation method of the glass material resistant to temperature change mainly includes the following preparation steps:

[0012] (1) Take 20 - 30 parts of whisker silicon, 40 - 50 parts of nano - silica, 2 - 4 parts of lithium oxide, 2 - 3 parts of sodium carbonate, and 4 - 5 parts of titanium dioxide by mass. Immerse the whisker silicon in an aluminum hydroxide solution for 2 - 3 min, take it out, add nano - silica, lithium oxide, sodium carbonate, and titanium dioxide, keep it warm at 1600 - 1700 °C for 2 - 4 h to obtain a glass melt. Pour the glass melt onto a graphite heating plate to form a plate, transfer it to an annealing furnace at 500 - 600 °C for annealing for 100 - 140 min, and naturally cool it to room temperature to obtain glass;

[0013] (2) Mix alumina, ethanol solution, and 3 - aminopropyltrimethoxysilane in a mass ratio of 1:80 - 100:0.3 - 0.5, ultrasonicate for 25 - 35 min, stir at 50 - 70 °C and 200 - 300 r / min for 22 - 26 h, filter, wash with ethanol 3 - 5 times, and dry to obtain pre - modified alumina; Mix the pre - modified alumina and acetonitrile in a mass ratio of 1:10 - 12, add 4 - bromo - 2 - hydroxybenzaldehyde in an equimolar amount of 3 - aminopropyltrimethoxysilane, stir at 200 - 300 r / min for 14 - 18 h, filter, wash with ethanol 3 - 5 times, and dry to obtain modified alumina; Mix the modified alumina, 4 - aminopyridine, and acetone in a mass ratio of 1:0.1 - 0.2:8 - 10, stir at 50 - 60 °C and 200 - 300 r / min for 11 - 13 h, filter, wash with acetone 3 - 5 times, and dry to obtain functionalized alumina;

[0014] (3) Mix 2,2'-bis(trifluoromethyl)benzidine and methanol in a mass ratio of 1:5 - 7, stir at

[0015] 200 - 300 r / min under nitrogen protection for 10 - 20 min, heat up to 50 - 55 °C, and uniformly add diethyl maleate in a molar amount 2 times that of 2,2'-bis(trifluoromethyl)benzidine within 8 - 10 min, then heat up to

[0016] 75 - 85 °C, continue to stir for 34 - 36 h, and dry at 50 - 60 °C for 22 - 24 h to obtain a functionalized monomer;

[0017] (4) Mix 4',4”(5”)-diaminodibenzo-15-crown-5 and methanol at a mass ratio of 1:5 to 7, stir at 200 - 300 r / min under nitrogen protection for 10 - 20 min, heat up to 50 - 55 °C, and uniformly add diethyl maleate in an equimolar amount to 4',4”(5”)-diaminodibenzo-15-crown-5 within 8 - 10 min. Then heat up to 75 - 85 °C and continue stirring for 34 - 36 h. Dry at 50 - 60 °C for 22 - 24 h to obtain a capping agent.

[0018] (5) Mix polyaspartate ester resin F420, polyaspartate ester resin F524, hexamethylene diisocyanate-based polyisocyanate trimer, and tetrahydrofuran at a molar ratio of 1:1:1.8 - 2:8 - 10, stir at 50 - 70 °C and 200 - 300 r / min for 50 - 70 min, cool down to 40 - 60 °C, continue stirring, and uniformly add a mixed solution 3 - 4 times the molar amount of polyaspartate ester resin F420 within 8 - 10 min. Then cool down to 30 - 50 °C and continue stirring for 2 - 4 h to obtain a modified polyurea.

[0019] (6) Mix the modified polyurea and functionalized alumina at a mass ratio of 1:0.15 - 0.25, stir at 30 - 50 °C and 200 - 300 r / min for 4 - 6 min to obtain a coating material. Spray it on the glass surface, vacuum dry at 50 - 70 °C for 70 - 74 h, and let it stand at room temperature for 70 - 74 h to obtain a temperature-resistant glass.

[0020] As an optimization, the length of the whisker silicon in step (1) is 1 - 5 μm.

[0021] As an optimization, the aluminum hydroxide solution in step (1) is prepared by mixing aluminum hydroxide and water evenly at a mass ratio of 1:3 - 5.

[0022] As an optimization, the thickness of the board in step (1) is 18 - 22 mm.

[0023] As an optimization, the ethanol solution in step (2) is prepared by mixing ethanol and water evenly at a mass ratio of 1:1.

[0024] As an optimization, the specific operation of drying in step (2) is vacuum drying at -10 - 0 °C for 22 - 26 h.

[0025] As an optimization, the mixed solution in step (5) is prepared by mixing a functional monomer, a capping agent, and tetrahydrofuran evenly at a molar ratio of 3 - 5:1:8 - 10.

[0026] As an optimization, the spraying thickness of the coating material in step (6) is 2 mm.

[0027] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:

[0028] When preparing the temperature-resistant glass material of the present invention, whisker silicon is immersed in an aluminum hydroxide solution, and then heated, mixed, and annealed with nano-silica, lithium oxide, sodium carbonate, and titanium dioxide to obtain glass; alumina is successively reacted with 3-aminopropyltrimethoxysilane, 4-bromo-2-hydroxybenzaldehyde, and 4-aminopyridine to obtain functionalized alumina; 2,2'-bis(trifluoromethyl)diaminobiphenyl and diethyl maleate are reacted to obtain a functionalized monomer; 4',4”(5”)-diaminodibenzo-15-crown-5 and diethyl maleate are reacted to obtain a capping agent; polyaspartate ester resin F420, polyaspartate ester resin F524, hexamethylene diisocyanate-based polyisocyanate trimer, functionalized monomer, and capping agent are reacted to obtain a modified polyurea; the modified polyurea is mixed with functionalized alumina to obtain a coating material, which is sprayed on the glass surface and dried to obtain the temperature-resistant glass material.

[0029] First, whisker silicon is immersed in an aluminum hydroxide solution, and then heated, mixed, and annealed with nano-silica, lithium oxide, sodium carbonate, and titanium dioxide to obtain glass; alumina is successively reacted with 3-aminopropyltrimethoxysilane, 4-bromo-2-hydroxybenzaldehyde, and 4-aminopyridine to obtain functionalized alumina; aluminum hydroxide is loaded on the surface of whisker silicon, and at high temperature, aluminum hydroxide is transformed into alumina, which can reduce the thermal expansion coefficient of the glass, thereby achieving the effect of temperature resistance; as an inorganic non-metallic material, alumina can enhance the heat conduction ability of the material, react with 3-aminopropyltrimethoxysilane to make its surface rich in amino groups, and then react with 4-bromo-2-hydroxybenzaldehyde, and part of it can form a conjugated ring, so that the coating has an anti-aging effect; reacting with 4-aminopyridine can form a ligand that achieves a host-guest effect with the crown ether, so as to achieve a better binding effect with the polyurea and endow the coating with self-healing ability.

[0030] Secondly, react 2,2'-bis(trifluoromethyl)benzidine with diethyl maleate to obtain a functional monomer; react 4',4”(5”)-diaminodibenzo-15-crown-5 with diethyl maleate to obtain a capping agent; react a polyaspartate resin F420, a polyaspartate resin F524, a hexamethylene diisocyanate-based polyisocyanate trimer, the functional monomer and the capping agent to obtain a modified polyurea; mix the modified polyurea with functionalized alumina to obtain a coating material, spray it on the glass surface, and dry it to obtain a temperature-resistant glass material. Fluorine atoms have extremely strong electronegativity, resulting in a relatively large bond energy of the carbon-fluorine bond and an extremely low surface tension, enabling the modified polyurea to form a dense protective film on the material surface, thereby preventing the penetration of water, oil, and stains and achieving an anti-fouling effect; due to the presence of crown ether on the prepared modified polyurea, it can achieve a better binding effect with functionalized alumina and endow the coating with self-healing ability. The polyurea coating often exhibits a high failure strain when subjected to impact loads, thereby absorbing or dissipating the huge energy generated by the impact loads, so that the material has impact resistance. Detailed implementation mode

[0031] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0032] Example 1:

[0033] A preparation method of a temperature-resistant glass material mainly includes the following preparation steps:

[0034] (1) Take 25 parts of whisker silicon, 40 parts of nano-silica, 2 parts of lithium oxide, 2 parts of sodium carbonate, and 4 parts of titanium dioxide by mass. Immerse the whisker silicon in an aluminum hydroxide solution for 2 min, take it out, add nano-silica, lithium oxide, sodium carbonate, and titanium dioxide, and keep it at 1600 °C for 2 h to obtain a glass melt. Pour the glass melt onto a graphite heating plate to make a plate, transfer it to an annealing furnace at 500 °C for annealing for 100 min, and naturally cool it to room temperature to obtain glass.

[0035] (2) Mix alumina, ethanol solution, and 3-aminopropyltrimethoxysilane in a mass ratio of 1:80:0.3, ultrasonicate for 25 min, stir at 50 °C and 200 r / min for 22 h, filter, wash with ethanol 3 times, and dry to obtain pre-modified alumina; Mix the pre-modified alumina and acetonitrile in a mass ratio of 1:10, add 4-bromo-2-hydroxybenzaldehyde in an equimolar amount of 3-aminopropyltrimethoxysilane, stir at 200 r / min for 14 h, filter, wash with ethanol 3 times, and dry to obtain modified alumina; Mix the modified alumina, 4-aminopyridine, and acetone in a mass ratio of 1:0.1:8, stir at 50 °C and 200 r / min for 11 h, filter, wash with acetone 3 times, and dry to obtain functionalized alumina;

[0036] (3) Mix 2,2'-bis(trifluoromethyl)benzidine and methanol in a mass ratio of 1:5, stir at 200 r / min under nitrogen protection for 10 min, heat up to 50 °C, and uniformly add diethyl maleate in a molar amount 2 times that of 2,2'-bis(trifluoromethyl)benzidine within 8 min, heat up to 75 °C, continue to stir for 34 h, and dry at 50 °C for 22 h to obtain a functionalized monomer;

[0037] (4) Mix 4',4”(5”)-diaminodibenzo-15-crown-5 and methanol in a mass ratio of 1:5, stir at 200 r / min under nitrogen protection for 10 min, heat up to 50 °C, and uniformly add diethyl maleate in an equimolar amount of 4',4”(5”)-diaminodibenzo-15-crown-5 within 8 min, heat up to 75 °C, continue to stir for 34 h, and dry at 50 °C for 22 h to obtain a capping agent;

[0038] (5) Mix polyaspartate resin F420, polyaspartate resin F524, hexamethylene diisocyanate-based polyisocyanate trimer, and tetrahydrofuran in a molar ratio of 1:1:1.8:8, stir at 50 °C and 200 r / min for 50 min, cool down to 40 °C, continue to stir, and uniformly add a mixed solution in a molar amount 3 times that of polyaspartate resin F420 within 8 min, cool down to 30 °C, and continue to stir for 2 h to obtain modified polyurea;

[0039] (6) Mix the modified polyurea and functionalized alumina in a mass ratio of 1:0.15, stir at 30 °C and 200 r / min for 4 min to obtain a coating material, spray it on the glass surface, vacuum dry at 50 °C for 70 h, and let it stand at room temperature for 70 h to obtain temperature-resistant glass.

[0040] The length of the whisker silicon described in step (1) is 1 μm.

[0041] The aluminum hydroxide solution described in step (1) is prepared by mixing aluminum hydroxide and water in a mass ratio of 1:3 and stirring evenly.

[0042] The thickness of the sheet described in step (1) is 18 mm.

[0043] The ethanol solution described in step (2) is prepared by mixing ethanol and water in a mass ratio of 1:1 and stirring evenly.

[0044] The specific operation of drying described in step (2) is vacuum drying at -10°C for 22 h.

[0045] The mixed solution described in step (5) is prepared by mixing a functional monomer, a capping agent, and tetrahydrofuran in a molar ratio of 3:1:8 and stirring evenly.

[0046] The spraying thickness of the coating material described in step (6) is 2 mm.

[0047] Example 2:

[0048] A preparation method of a temperature-resistant glass material mainly includes the following preparation steps:

[0049] (1) Take 25 parts of whisker silicon, 45 parts of nano-silica, 3 parts of lithium oxide, 2.5 parts of sodium carbonate, and 4.5 parts of titanium dioxide by mass. Immerse the whisker silicon in the aluminum hydroxide solution for 2.5 min, take it out, add nano-silica, lithium oxide, sodium carbonate, and titanium dioxide, keep it at 1650°C for 3 h to obtain a glass melt, pour the glass melt onto a graphite heating plate to form a sheet, transfer it to an annealing furnace at 550°C for annealing for 120 min, and naturally cool to room temperature to obtain glass;

[0050] (2) Mix alumina, ethanol solution, and 3-aminopropyltrimethoxysilane in a mass ratio of 1:90:0.4, ultrasonically for 30 min, stir at 60°C and 250 r / min for 24 h, filter, wash with ethanol 4 times, dry to obtain pre-modified alumina; Mix the pre-modified alumina and acetonitrile in a mass ratio of 1:11, add 4-bromo-2-hydroxybenzaldehyde in an equimolar amount of 3-aminopropyltrimethoxysilane, stir at 250 r / min for 16 h, filter, wash with ethanol 4 times, dry to obtain modified alumina; Mix the modified alumina, 4-aminopyridine, and acetone in a mass ratio of 1:0.15:9, stir at 55°C and 250 r / min for 12 h, filter, wash with acetone 4 times, dry to obtain functionalized alumina;

[0051] (3) Mix 2,2'-bis(trifluoromethyl)benzidine and methanol in a mass ratio of 1:6, at

[0052] At 250 r / min, under nitrogen protection, stir for 15 min, heat up to 52.5 °C, and uniformly add diethyl maleate in an amount twice the molar amount of 2,2'-bis(trifluoromethyl)benzidine diamine within 9 min. Then heat up to 80 °C and continue stirring for 35 h. Dry at 55 °C for 23 h to obtain the functional monomer;

[0053] (4) Mix 4',4”(5”)-diaminodibenzo-15-crown-5 and methanol at a mass ratio of 1:6. At 250 r / min, under nitrogen protection, stir for 15 min, heat up to 52.5 °C, and uniformly add diethyl maleate in an amount equal to the molar amount of 4',4”(5”)-diaminodibenzo-15-crown-5 within 9 min. Then heat up to 80 °C and continue stirring for 35 h. Dry at 55 °C for 23 h to obtain the end-capping agent;

[0054] (5) Mix polyaspartate ester resin F420, polyaspartate ester resin F524, hexamethylene diisocyanate-based polyisocyanate trimer, and tetrahydrofuran at a molar ratio of 1:1:1.9:9. Stir at 60 °C and 250 r / min for 60 min, then cool down to 50 °C and continue stirring. Uniformly add a mixed solution in an amount 3.5 times the molar amount of polyaspartate ester resin F420 within 9 min, then cool down to 40 °C and continue stirring for 3 h to obtain the modified polyurea;

[0055] (6) Mix the modified polyurea and functionalized alumina at a mass ratio of 1:0.2. Stir at 40 °C and 250 r / min for 5 min to obtain the coating material. Spray it on the glass surface, dry it in vacuum at 60 °C for 72 h, and let it stand at room temperature for 72 h to obtain the temperature-resistant glass.

[0056] The length of the whisker silicon described in step (1) is 3 μm.

[0057] The aluminum hydroxide solution described in step (1) is prepared by mixing aluminum hydroxide and water evenly at a mass ratio of 1:4.

[0058] The thickness of the board described in step (1) is 20 mm.

[0059] The ethanol solution described in step (2) is prepared by mixing ethanol and water evenly at a mass ratio of 1:1.

[0060] The specific operation of drying described in step (2) is to dry in vacuum at -5 °C for 24 h.

[0061] The mixed solution described in step (5) is prepared by mixing the functional monomer, the end-capping agent, and tetrahydrofuran evenly at a molar ratio of 4:1:9.

[0062] The spraying thickness of the coating material described in step (6) is 2 mm.

[0063] Example 3:

[0064] A preparation method of a temperature-resistant glass material mainly includes the following preparation steps:

[0065] (1) Take 30 parts of whisker silicon, 50 parts of nano-silica, 4 parts of lithium oxide, 3 parts of sodium carbonate, and 5 parts of titanium dioxide by mass. Immerse the whisker silicon in an aluminum hydroxide solution for 3 min, take it out, add nano-silica, lithium oxide, sodium carbonate, and titanium dioxide, keep it at 1700 °C for 4 h to obtain a glass melt. Pour the glass melt onto a graphite heating plate to form a plate, transfer it to an annealing furnace at 600 °C for annealing for 140 min, and naturally cool to room temperature to obtain the glass;

[0066] (2) Mix alumina, ethanol solution, and 3-aminopropyltrimethoxysilane in a mass ratio of 1:100:0.5, ultrasonicate for 35 min, stir at 70 °C and 300 r / min for 26 h, filter, wash with ethanol 5 times, and dry to obtain pre-modified alumina; Mix the pre-modified alumina and acetonitrile in a mass ratio of 1:12, add 4-bromo-2-hydroxybenzaldehyde in an equimolar amount of 3-aminopropyltrimethoxysilane, stir at 300 r / min for 18 h, filter, wash with ethanol 5 times, and dry to obtain modified alumina; Mix the modified alumina, 4-aminopyridine, and acetone in a mass ratio of 1:0.2:10, stir at 60 °C and 300 r / min for 13 h, filter, wash with acetone 5 times, and dry to obtain functionalized alumina;

[0067] (3) Mix 2,2'-bis(trifluoromethyl)benzidine and methanol in a mass ratio of 1:7, stir at 300 r / min under nitrogen protection for 20 min, raise the temperature to 55 °C, and uniformly add diethyl maleate in a molar amount 2 times that of 2,2'-bis(trifluoromethyl)benzidine within 10 min. Raise the temperature to 85 °C and continue to stir for 36 h, and dry at 60 °C for 24 h to obtain a functionalized monomer;

[0068] (4) Mix 4',4”(5”)-diaminodibenzo-15-crown-5 and methanol in a mass ratio of 1:7, stir at 300 r / min under nitrogen protection for 20 min, raise the temperature to 55 °C, and uniformly add diethyl maleate in an equimolar amount of 4',4”(5”)-diaminodibenzo-15-crown-5 within 10 min. Raise the temperature to 85 °C and continue to stir for 36 h, and dry at 60 °C for 24 h to obtain a capping agent;

[0069] (5) Mix polyaspartate resin F420, polyaspartate resin F524, hexamethylene diisocyanate-based polyisocyanate trimer, and tetrahydrofuran in a molar ratio of 1:1:2:10, stir at 70 °C and 300 r / min for 70 min, cool down to 60 °C, continue stirring, and uniformly add a mixed solution that is 4 times the molar amount of polyaspartate resin F420 within 10 min. Then cool down to 50 °C and continue stirring for 4 h to obtain a modified polyurea.

[0070] (6) Mix the modified polyurea and functionalized alumina in a mass ratio of 1:0.25, stir at 50 °C and 300 r / min for 6 min to obtain a coating material. Spray the coating material on the glass surface, dry it in vacuum at 70 °C for 74 h, and let it stand at room temperature for 74 h to obtain a temperature-resistant glass.

[0071] The length of the whisker silicon described in step (1) is 5 μm.

[0072] The aluminum hydroxide solution described in step (1) is prepared by uniformly mixing aluminum hydroxide and water in a mass ratio of 1:5.

[0073] The thickness of the plate described in step (1) is 22 mm.

[0074] The ethanol solution described in step (2) is prepared by uniformly mixing ethanol and water in a mass ratio of 1:1.

[0075] The specific operation of drying described in step (2) is vacuum drying at 0 °C for 26 h.

[0076] The mixed solution described in step (5) is prepared by uniformly mixing a functional monomer, a capping agent, and tetrahydrofuran in a molar ratio of 5:1:10.

[0077] The spraying thickness of the coating material described in step (6) is 2 mm.

[0078] Comparative Example 1:

[0079] A preparation method of a temperature-resistant glass material mainly includes the following preparation steps:

[0080] (1) Take 25 parts of whisker silicon, 45 parts of nano-silica, 3 parts of lithium oxide, 2.5 parts of sodium carbonate, and 4.5 parts of titanium dioxide by mass. Mix whisker silicon, nano-silica, lithium oxide, sodium carbonate, and titanium dioxide, keep it at 1650 °C for 3 h to obtain a glass melt. Pour the glass melt onto a graphite heating plate to form a plate, transfer it to an annealing furnace at 550 °C for annealing for 120 min, and naturally cool it to room temperature to obtain a glass.

[0081] (2) Mix alumina, ethanol solution, and 3-aminopropyltrimethoxysilane in a mass ratio of 1:90:0.4, ultrasonicate for 30 min, stir at 60 °C and 250 r / min for 24 h, filter, wash with ethanol 4 times, and dry to obtain pre-modified alumina; mix the pre-modified alumina and acetonitrile in a mass ratio of 1:11, add 4-bromo-2-hydroxybenzaldehyde in an equimolar amount of 3-aminopropyltrimethoxysilane, stir at 250 r / min for 16 h, filter, wash with ethanol 4 times, and dry to obtain modified alumina; mix the modified alumina, 4-aminopyridine, and acetone in a mass ratio of 1:0.15:9, stir at 55 °C and 250 r / min for 12 h, filter, wash with acetone 4 times, and dry to obtain functionalized alumina;

[0082] (3) Mix 2,2'-bis(trifluoromethyl)benzidine and methanol in a mass ratio of 1:6, stir at 250 r / min under nitrogen protection for 15 min, raise the temperature to 52.5 °C, and uniformly add diethyl maleate in a molar amount 2 times that of 2,2'-bis(trifluoromethyl)benzidine within 9 min, raise the temperature to 80 °C, continue stirring for 35 h, and dry at 55 °C for 23 h to obtain a functionalized monomer;

[0083]

[0084] (4) Mix 4',4”(5”)-diaminodibenzo-15-crown-5 and methanol in a mass ratio of 1:6, stir at 250 r / min under nitrogen protection for 15 min, raise the temperature to 52.5 °C, and uniformly add diethyl maleate in an equimolar amount of 4',4”(5”)-diaminodibenzo-15-crown-5 within 9 min, raise the temperature to 80 °C, continue stirring for 35 h, and dry at 55 °C for 23 h to obtain a capping agent;

[0085] (5) Mix polyaspartate resin F420, polyaspartate resin F524, hexamethylene diisocyanate-based polyisocyanate trimer, and tetrahydrofuran in a molar ratio of 1:1:1.9:9, stir at 60 °C and 250 r / min for 60 min, cool to 50 °C, continue stirring, and uniformly add a mixed solution in a molar amount 3.5 times that of polyaspartate resin F420 within 9 min, cool to 40 °C, and continue stirring for 3 h to obtain a modified polyurea;

[0086] (6) Mix the modified polyurea and functionalized alumina in a mass ratio of 1:0.2, stir at 40 °C and 250 r / min for 5 min to obtain a coating material, spray it on the glass surface, vacuum dry at 60 °C for 72 h, and let it stand at room temperature for 72 h to obtain temperature-resistant glass.

[0087] The length of the whisker silicon described in step (1) is 3 μm.

[0088] The thickness of the sheet in step (1) is 20 mm.

[0089] The ethanol solution in step (2) is prepared by mixing ethanol and water evenly at a mass ratio of 1:1.

[0090] The specific operation of drying in step (2) is vacuum drying at -5°C for 24 h.

[0091] The mixed solution in step (5) is prepared by mixing the functional monomer, the capping agent and tetrahydrofuran evenly at a molar ratio of 4:1:9.

[0092] The spraying thickness of the coating material in step (6) is 2 mm.

[0093] Comparative Example 2

[0094] A preparation method of a temperature-resistant glass material mainly includes the following preparation steps:

[0095] (1) Take 25 parts of whisker silicon, 45 parts of nano-silica, 3 parts of lithium oxide, 2.5 parts of sodium carbonate, and 4.5 parts of titanium dioxide by mass. Immerse the whisker silicon in the aluminum hydroxide solution for 2.5 min, take it out, add nano-silica, lithium oxide, sodium carbonate and titanium dioxide, keep it warm at 1650°C for 3 h to obtain the glass liquid. Pour the glass liquid onto the graphite heating plate to make a sheet, transfer it to an annealing furnace at 550°C for annealing for 120 min, and cool it naturally to room temperature to obtain the glass;

[0096] (2) Mix alumina, ethanol solution and 3-aminopropyltrimethoxysilane at a mass ratio of 1:90:0.4, ultrasonically for 30 min, stir at 60°C and 250 r / min for 24 h, filter, wash with ethanol 4 times, and dry to obtain pre-modified alumina; Mix the pre-modified alumina and acetonitrile at a mass ratio of 1:11, add 4-bromo-2-hydroxybenzaldehyde in an equimolar amount of 3-aminopropyltrimethoxysilane, stir at 250 r / min for 16 h, filter, wash with ethanol 4 times, and dry to obtain modified alumina;

[0097] (3) Mix 2,2'-bis(trifluoromethyl)diaminobiphenyl and methanol at a mass ratio of 1:6, stir at 250 r / min under nitrogen protection for 15 min, heat up to 52.5°C, and uniformly add diethyl maleate twice the molar amount of 2,2'-bis(trifluoromethyl)diaminobiphenyl within 9 min, heat up to 80°C, continue to stir for 35 h, and dry at 55°C for 23 h to obtain the functional monomer;

[0098] (4) Mix 4',4”(5”)-diaminodibenzo-15-crown-5 and methanol at a mass ratio of 1:6, stir at 250 r / min under nitrogen protection for 15 min, heat up to 52.5 °C, and uniformly add diethyl maleate in an amount equimolar to 4',4”(5”)-diaminodibenzo-15-crown-5 within 9 min. Then heat up to 80 °C and continue stirring for 35 h. Dry at 55 °C for 23 h to obtain a capping agent.

[0099] (5) Mix polyaspartate ester resin F420, polyaspartate ester resin F524, hexamethylene diisocyanate-based polyisocyanate trimer, and tetrahydrofuran at a molar ratio of 1:1:1.9:9, stir at 60 °C and 250 r / min for 60 min, cool down to 50 °C and continue stirring. Uniformly add a mixture in an amount 3.5 times the molar amount of polyaspartate ester resin F420 within 9 min, then cool down to 40 °C and continue stirring for 3 h to obtain a modified polyurea.

[0100] (6) Mix the modified polyurea and modified alumina at a mass ratio of 1:0.2, stir at 40 °C and 250 r / min for 5 min to obtain a coating material. Spray it on the glass surface, dry it in vacuum at 60 °C for 72 h, and let it stand at room temperature for 72 h to obtain a temperature-resistant glass.

[0101] The length of the whisker silicon described in step (1) is 3 μm.

[0102] The aluminum hydroxide solution described in step (1) is prepared by mixing aluminum hydroxide and water evenly at a mass ratio of 1:4.

[0103] The thickness of the board described in step (1) is 20 mm.

[0104] The ethanol solution described in step (2) is prepared by mixing ethanol and water evenly at a mass ratio of 1:1.

[0105] The specific operation of drying described in step (2) is to dry in vacuum at -5 °C for 24 h.

[0106] The mixture described in step (5) is prepared by mixing a functional monomer, a capping agent, and tetrahydrofuran evenly at a molar ratio of 4:1:9.

[0107] The spraying thickness of the coating material described in step (6) is 2 mm. Comparative Example 3

[0108] A preparation method of a temperature-resistant glass material mainly includes the following preparation steps:

[0109] (1) Take 25 parts of whisker silicon, 45 parts of nano-silica, 3 parts of lithium oxide, 2.5 parts of sodium carbonate, and 4.5 parts of titanium dioxide by mass. Immerse the whisker silicon in an aluminum hydroxide solution for 2.5 min, take it out, add nano-silica, lithium oxide, sodium carbonate, and titanium dioxide, keep it at 1650 °C for 3 h to obtain a glass melt. Pour the glass melt onto a graphite heating plate to form a plate, transfer it to an annealing furnace at 550 °C for annealing for 120 min, and naturally cool it to room temperature to obtain the glass;

[0110] (2) Mix 2,2'-bis(trifluoromethyl)benzidine and methanol in a mass ratio of 1:6, stir at 250 r / min under nitrogen protection for 15 min, heat up to 52.5 °C, and uniformly add diethyl maleate with a molar amount twice that of 2,2'-bis(trifluoromethyl)benzidine within 9 min. Heat up to 80 °C and continue stirring for 35 h, and dry at 55 °C for 23 h to obtain a functional monomer;

[0111]

[0112] (3) Mix 4',4”(5”)-diaminodibenzo-15-crown-5 and methanol in a mass ratio of 1:6, stir at 250 r / min under nitrogen protection for 15 min, heat up to 52.5 °C, and uniformly add diethyl maleate with an equimolar amount of 4',4”(5”)-diaminodibenzo-15-crown-5 within 9 min. Heat up to 80 °C and continue stirring for 35 h, and dry at 55 °C for 23 h to obtain a capping agent;

[0113] (4) Mix polyaspartate resin F420, polyaspartate resin F524, hexamethylene diisocyanate-based polyisocyanate trimer, and tetrahydrofuran in a molar ratio of 1:1:1.9:9, stir at 60 °C and 250 r / min for 60 min, cool down to 50 °C, continue stirring, and uniformly add a mixture with a molar amount 3.5 times that of polyaspartate resin F420 within 9 min. Cool down to 40 °C and continue stirring for 3 h to obtain a modified polyurea;

[0114] (5) Mix the modified polyurea and alumina in a mass ratio of 1:0.2, stir at 40 °C and 250 r / min for 5 min to obtain a coating material, spray it on the glass surface, vacuum dry it at 60 °C for 72 h, and let it stand at room temperature for 72 h to obtain the temperature-resistant glass.

[0115] The length of the whisker silicon described in step (1) is 3 μm.

[0116] The aluminum hydroxide solution described in step (1) is prepared by uniformly mixing aluminum hydroxide and water in a mass ratio of 1:4.

[0117] The thickness of the plate described in step (1) is 20 mm.​

[0118] The mixed solution described in step (4) is prepared by uniformly mixing a functional monomer, a capping agent, and tetrahydrofuran in a molar ratio of 4:1:9.

[0119] The spraying thickness of the coating material described in step (5) is 2 mm.

[0120] Comparative Example 4:

[0121] A preparation method of a temperature-resistant glass material mainly includes the following preparation steps:

[0122] (1) Take 25 parts of whisker silicon, 45 parts of nano-silica, 3 parts of lithium oxide, 2.5 parts of sodium carbonate, and 4.5 parts of titanium dioxide by mass. Immerse the whisker silicon in an aluminum hydroxide solution for 2.5 min, take it out, add nano-silica, lithium oxide, sodium carbonate, and titanium dioxide, keep it at 1650 °C for 3 h to obtain a glass liquid. Pour the glass liquid onto a graphite heating plate to make a plate, transfer it to an annealing furnace at 550 °C for annealing for 120 min, and naturally cool it to room temperature to obtain glass;

[0123] (2) Mix 2,2'-bis(trifluoromethyl)benzidine and methanol in a mass ratio of 1:6, stir at 250 r / min under nitrogen protection for 15 min, heat up to 52.5 °C, and uniformly add diethyl maleate, which is 2 times the molar amount of 2,2'-bis(trifluoromethyl)benzidine, within 9 min. Heat up to 80 °C and continue stirring for 35 h, and dry at 55 °C for 23 h to obtain a functional monomer;

[0124] 250 r / min, under nitrogen protection, stir for 15 min, heat up to 52.5 °C, and uniformly add diethyl maleate, which is 2 times the molar amount of 2,2'-bis(trifluoromethyl)benzidine, within 9 min. Heat up to 80 °C and continue stirring for 35 h, and dry at 55 °C for 23 h to obtain a functional monomer;

[0125] (3) Mix 4',4”(5”)-diaminodibenzo-15-crown-5 and methanol in a mass ratio of 1:6, stir at 250 r / min under nitrogen protection for 15 min, heat up to 52.5 °C, and uniformly add diethyl maleate, which is equimolar to 4',4”(5”)-diaminodibenzo-15-crown-5, within 9 min. Heat up to 80 °C and continue stirring for 35 h, and dry at 55 °C for 23 h to obtain a capping agent;

[0126] (4) Mix polyaspartic ester resin F420, polyaspartic ester resin F524, hexamethylene diisocyanate-based polyisocyanate trimer, and tetrahydrofuran in a molar ratio of 1:1:1.9:9, stir at 60 °C and 250 r / min for 60 min, cool down to 50 °C, continue stirring, and uniformly add a mixed solution, which is 3.5 times the molar amount of polyaspartic ester resin F420, within 9 min. Cool down to 40 °C and continue stirring for 3 h to obtain a modified polyurea;

[0127] (5) Stir the modified polyurea at 40 °C and 250 r / min for 5 min to obtain a coating material, spray it on the glass surface, vacuum dry it at 60 °C for 72 h, and let it stand at room temperature for 72 h to obtain temperature-resistant glass.

[0128] The length of the whisker silicon described in step (1) is 3 μm.

[0129] The aluminum hydroxide solution described in step (1) is prepared by mixing aluminum hydroxide and water evenly at a mass ratio of 1:4.

[0130] The thickness of the board described in step (1) is 20 mm.

[0131] The mixed solution described in step (4) is prepared by mixing the functional monomer, the capping agent and tetrahydrofuran evenly at a molar ratio of 4:1:9.

[0132] The spraying thickness of the coating material described in step (5) is 2 mm.

[0133] Comparative Example 5:

[0134] A preparation method of a temperature-resistant glass material mainly includes the following preparation steps:

[0135] (1) Take 25 parts of whisker silicon, 45 parts of nano-silica, 3 parts of lithium oxide, 2.5 parts of sodium carbonate, and 4.5 parts of titanium dioxide by mass. Immerse the whisker silicon in the aluminum hydroxide solution for 2.5 min, take it out, add nano-silica, lithium oxide, sodium carbonate and titanium dioxide, keep it at 1650 °C for 3 h to obtain a glass liquid, pour the glass liquid onto a graphite heating plate, make it into a board, transfer it to an annealing furnace at 550 °C for annealing for 120 min, and naturally cool it to room temperature to obtain glass;

[0136] (2) Mix alumina, ethanol solution and 3-aminopropyltrimethoxysilane at a mass ratio of 1:90:0.4, ultrasonicate for 30 min, stir at 60 °C and 250 r / min for 24 h, filter, wash with ethanol 4 times, dry to obtain pre-modified alumina; Mix the pre-modified alumina and acetonitrile at a mass ratio of 1:11, add 4-bromo-2-hydroxybenzaldehyde in an equimolar amount of 3-aminopropyltrimethoxysilane, stir at 250 r / min for 16 h, filter, wash with ethanol 4 times, dry to obtain modified alumina; Mix the modified alumina, 4-aminopyridine and acetone at a mass ratio of 1:0.15:9, stir at 55 °C and 250 r / min for 12 h, filter, wash with acetone 4 times, dry to obtain functionalized alumina;

[0137] (3) Mix 4',4”(5”)-diaminodibenzo-15-crown-5 and methanol in a mass ratio of 1:6, stir at 250 r / min under nitrogen protection for 15 min, heat up to 52.5 °C, and uniformly add diethyl maleate in an equimolar amount of 4',4”(5”)-diaminodibenzo-15-crown-5 within 9 min. Then heat up to 80 °C and continue stirring for 35 h, and dry at 55 °C for 23 h to obtain a capping agent;

[0138] (4) Mix polyaspartate resin F420, polyaspartate resin F524, hexamethylene diisocyanate-based polyisocyanate trimer, and tetrahydrofuran in a molar ratio of 1:1:1.9:9, stir at 60 °C and 250 r / min for 60 min, cool down to 50 °C, continue stirring, and uniformly add a mixed solution 3.5 times the molar amount of polyaspartate resin F420 within 9 min. Then cool down to 40 °C and continue stirring for 3 h to obtain a modified polyurea;

[0139] (5) Mix the modified polyurea and functionalized alumina in a mass ratio of 1:0.2, stir at 40 °C and 250 r / min for 5 min to obtain a coating material, spray it on the glass surface, vacuum dry at 60 °C for 72 h, and let it stand at room temperature for 72 h to obtain a temperature-resistant glass.

[0140] The length of the whisker silicon described in step (1) is 3 μm.

[0141] The aluminum hydroxide solution described in step (1) is prepared by mixing aluminum hydroxide and water evenly in a mass ratio of 1:4.

[0142] The thickness of the plate described in step (1) is 20 mm.

[0143] The ethanol solution described in step (2) is prepared by mixing ethanol and water evenly in a mass ratio of 1:1.

[0144] The specific operation of drying described in step (2) is vacuum drying at -5 °C for 24 h.

[0145] The mixed solution described in step (4) is prepared by mixing the capping agent and tetrahydrofuran evenly in a molar ratio of 1:9.

[0146] The spraying thickness of the coating material described in step (5) is 2 mm.

[0147] Comparative Example 6:

[0148] A preparation method of a temperature-resistant glass material mainly includes the following preparation steps:

[0149] (1) Take 25 parts of whisker silicon, 45 parts of nano-silica, 3 parts of lithium oxide, 2.5 parts of sodium carbonate, and 4.5 parts of titanium dioxide by mass. Immerse the whisker silicon in an aluminum hydroxide solution for 2.5 min, take it out, add nano-silica, lithium oxide, sodium carbonate, and titanium dioxide, and keep it at 1650 °C for 3 h to obtain a glass melt. Pour the glass melt onto a graphite heating plate to form a plate, transfer it to an annealing furnace at 550 °C for annealing for 120 min, and cool it naturally to room temperature to obtain glass;

[0150] (2) Mix alumina, ethanol solution, and 3-aminopropyltrimethoxysilane at a mass ratio of 1:90:0.4, ultrasonicate for 30 min, stir at 60 °C and 250 r / min for 24 h, filter, wash with ethanol 4 times, and dry to obtain pre-modified alumina; Mix the pre-modified alumina and acetonitrile at a mass ratio of 1:11, add 4-bromo-2-hydroxybenzaldehyde in an equimolar amount of 3-aminopropyltrimethoxysilane, stir at 250 r / min for 16 h, filter, wash with ethanol 4 times, and dry to obtain modified alumina; Mix the modified alumina, 4-aminopyridine, and acetone at a mass ratio of 1:0.15:9, stir at 55 °C and 250 r / min for 12 h, filter, wash with acetone 4 times, and dry to obtain functionalized alumina;

[0151] (3) Mix 2,2'-bis(trifluoromethyl)benzidine and methanol at a mass ratio of 1:6, stir at 250 r / min under nitrogen protection for 15 min, heat up to 52.5 °C, and uniformly add diethyl maleate in a molar amount 2 times that of 2,2'-bis(trifluoromethyl)benzidine within 9 min, then heat up to 80 °C and continue stirring for 35 h, and dry at 55 °C for 23 h to obtain a functionalized monomer;

[0152] (4) Mix polyaspartate resin F420, polyaspartate resin F524, hexamethylene diisocyanate-based polyisocyanate trimer, and tetrahydrofuran at a molar ratio of 1:1:1.9:9, stir at 60 °C and 250 r / min for 60 min, cool down to 50 °C, continue stirring, and uniformly add a mixed solution with a molar amount 3.5 times that of polyaspartate resin F420 within 9 min, then cool down to 40 °C and continue stirring for 3 h to obtain modified polyurea;

[0153] (5) Mix the modified polyurea and functionalized alumina at a mass ratio of 1:0.2, stir at 40 °C and 250 r / min for 5 min to obtain a coating material, spray it on the glass surface, vacuum dry at 60 °C for 72 h, and let it stand at room temperature for 72 h to obtain temperature-resistant glass.

[0154] The length of the whisker silicon described in step (1) is 3 μm.

[0155] The aluminum hydroxide solution described in step (1) is prepared by mixing aluminum hydroxide and water evenly at a mass ratio of 1:4.

[0156] The thickness of the plate described in step (1) is 20 mm.

[0157] The ethanol solution described in step (2) is prepared by mixing ethanol and water evenly at a mass ratio of 1:1.

[0158] The specific operation of drying described in step (2) is vacuum drying at -5°C for 24 h.

[0159] The mixed solution described in step (4) is prepared by mixing the functional monomer and tetrahydrofuran evenly at a molar ratio of 4:9.

[0160] The spraying thickness of the coating material described in step (5) is 2 mm.

[0161] Comparative Example 7:

[0162] A preparation method of a temperature-resistant glass material mainly includes the following preparation steps:

[0163] (1) Take 25 parts of whisker silicon, 45 parts of nano-silica, 3 parts of lithium oxide, 2.5 parts of sodium carbonate, and 4.5 parts of titanium dioxide by mass. Immerse the whisker silicon in the aluminum hydroxide solution for 2.5 min, take it out, add nano-silica, lithium oxide, sodium carbonate, and titanium dioxide, keep it warm at 1650°C for 3 h to obtain the glass liquid. Pour the glass liquid onto the graphite heating plate to make a plate, transfer it to an annealing furnace at 550°C for annealing for 120 min, and cool it naturally to room temperature to obtain the temperature-resistant glass;

[0164] The length of the whisker silicon described in step (1) is 3 μm.

[0165] The aluminum hydroxide solution described in step (1) is prepared by mixing aluminum hydroxide and water evenly at a mass ratio of 1:4.

[0166] The thickness of the plate described in step (1) is 20 mm.

[0167] Test Example 1:

[0168] Coating self-healing and aging resistance test:

[0169] Self-healing test method: Make the coating materials prepared in each example and comparative example into splines with a length of 10 mm, a width of 4 mm, and a thickness of 1 mm, conduct tensile property tests, test the tensile fracture strength at 5 mm / min, make a small cut with a length of 2 mm and a depth of 0.4 mm transversely on the same specimen, let it stand at room temperature for 24 h, and test the tensile fracture strength again, and calculate the repair efficiency, where the repair efficiency = tensile fracture strength after self-healing / tensile fracture strength before self-healing * 100%;

[0170] Aging resistance test method: The coating materials prepared in each example and comparative example were made into splines with a length of 10 mm, a width of 4 mm, and a thickness of 1 mm, and tensile property tests were carried out. The tensile fracture strength was tested at 5 mm / min, and the same specimens were irradiated under a fluorescent ultraviolet lamp UV-A340 for 15 days, and then the tensile fracture strength was tested, and the tensile fracture retention rate was calculated, where the tensile fracture retention rate = tensile fracture strength after aging / tensile fracture strength before aging * 100%. The results are shown in Table 1.

[0171] Table 1

[0172] Repair efficiency Retention rate of tensile fracture Example 1 98.6％ 98.5％ Example 2 99.1％ 98.9％ Example 3 98.9％ 98.8％ Comparative example 1 99.0％ 98.7％ Comparative example 2 74.5％ 98.4％ Comparative example 3 73.9％ 96.2％ Comparative example 4 74.0％ 95.9％ Comparative example 5 98.5％ 98.3％ Comparative example 6 75.1％ 98.6％ Comparative example 7 —— ——

[0173] From the comparison of the experimental data in Table 1, it can be found that the coating of the temperature-variable resistant glass material prepared by the present invention has good self-healing and aging resistance capabilities.

[0174] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 2 in Table 1, it can be found that the repair efficiency of Examples 1, 2, 3 is greater than that of Comparative Example 2, indicating that the modified alumina reacts with 4-aminopyridine to form a ligand that can achieve a host-guest effect with the crown ether on the polyurea, making the coating have the ability of self-healing;

[0175] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 3, it can be found that the tensile fracture retention rate of Examples 1, 2, 3 is greater than that of Comparative Example 3, indicating that alumina reacts with 3-aminopropyltrimethoxysilane to make its surface rich in amino groups, and then reacts with 4-bromo-2-hydroxybenzaldehyde to form a conjugated ring, thereby making the coating have an aging resistance effect.

[0176] Test Example 2:

[0177] Impact resistance test:

[0178] The glass prepared in each example and comparative example was made into a specimen with a thickness of 6 mm, a length of 220 mm, and a width of 220 mm by a water jet, and then the coating was sprayed, and it was left standing at room temperature for 7 d. The SHPB device of Southwest University of Science and Technology was used. The steel impact rod used in the test was a cylinder with a diameter of 20 mm, a length of 400 mm, and a weight of 0.96 kg, and the model was 60SiMnA. A laser velocimeter was installed at the entrance of the SHPB chamber to test the initial velocity of the impact rod leaving the chamber during the test. Strain gauges were longitudinally pasted at a position 60 mm from the center point along the diagonal of the back surface of the specimen. During the test, a dynamic acquisition instrument was used to collect real-time strain, and a high-speed camera was used to shoot at a frame rate of 20000 frames per second. The acquisition frequency of the dynamic acquisition instrument was 1 MHz, and the impact speed was 18 m / s. The maximum deformation value at the center was tested. The results are shown in Table 2.

[0179] Table 2

[0180] Maximum central deformation value Example 1 18.568 mm Example 2 18.235 mm Example 3 18.442 mm Comparative example 1 18.662 mm Comparative example 2 18.535 mm Comparative example 3 18.279 mm Comparative example 4 18.331 mm Comparative example 5 18.574 mm Comparative example 6 18.392 mm Comparative example 7 24.065 mm

[0181] From the comparison of the experimental data in Table 2, it can be found that the temperature-resistant glass material prepared by the present invention has good impact resistance.

[0182] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 7 in Table 2, it can be found that the maximum central deformation values of Examples 1, 2, and 3 are smaller than those of Comparative Example 7, indicating that the polyurea coating often exhibits a high failure strain when subjected to impact loads, thereby absorbing or dissipating the huge energy generated by the impact loads, thus enhancing the impact resistance of the material.

[0183] Test Example 3:

[0184] Thermal conductivity test:

[0185] Test by laser thermal conductivity meter: Calculate the specific heat capacity of the sample through a differential scanning calorimeter, and test the thermal diffusivity of the coating material through a laser thermal conductivity meter (LFA467). Make specimens with a length of 5 mm, a width of 5 mm, and a thickness of 2 mm from the coating materials of each example and comparative example. Before testing, spray graphite treatment on the surface of the sample, and calculate the thermal conductivity, where the thermal conductivity = sample thermal diffusivity * sample density * sample specific heat capacity, and test by differential scanning calorimeter. The results are shown in Table 3.

[0186] Table 3

[0187] Thermal conductivity Example 1 0.3869 W / (m·K) Example 2 0.3899 W / (m·K) Example 3 0.3842 W / (m·K) Comparative example 1 0.3829 W / (m·K) Comparative example 2 0.3874 W / (m·K) Comparative example 3 0.3860 W / (m·K) Comparative example 4 0.1487 W / (m·K) Comparative example 5 0.3837 W / (m·K) Comparative example 6 0.3885 W / (m·K) Comparative example 7 ——

[0188] From the comparison of the experimental data in Table 3, it can be found that the coating of the temperature-resistant glass material prepared by the present invention has good thermal conductivity.

[0189] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 4 in Table 3, it can be found that the thermal conductivity of Examples 1, 2, and 3 is larger than that of Comparative Example 4, indicating that alumina, as an inorganic non-metallic filler, can enhance the thermal conductivity of the coating.

[0190] Test Example 4:

[0191] Temperature change resistance test:

[0192] Test the thermal expansion coefficients of the glasses prepared in each example and comparative example in the temperature range of 30 - 500 °C through a thermal expansion coefficient measuring instrument. The results are shown in Table 4.

[0193] Table 4

[0194] Coefficient of thermal expansion Example 1 <![CDATA[0.3977×10 -6 K -1 > Example 2 <![CDATA[0.3915×10 -6 K -1 > Example 3 <![CDATA[0.3942×10 -6 K -1 > Comparative example 1 <![CDATA[0.5283×10 -6 K -1 > Comparative example 2 <![CDATA[0.3933×10 -6 K -1 > Comparative example 3 <![CDATA[0.3960×10 -6 K -1 > Comparative example 4 <![CDATA[0.3985×10 -6 K -1 > Comparative example 5 <![CDATA[0.3924×10 -6 K -1 > Comparative example 6 <![CDATA[0.3947×10 -6 K -1 > Comparative example 7 <![CDATA[0.3950×10 -6 K -1 >

[0195] From the comparison of the experimental data in Table 4, it can be found that the temperature-resistant glass material prepared by the present invention has good temperature change resistance.

[0196] From the comparison of the experimental data of Examples 1, 2, and 3 and Comparative Example 1 in Table 4, it can be found that the thermal expansion coefficients of Examples 1, 2, and 3 are smaller than that of Comparative Example 1, indicating that loading aluminum hydroxide on the surface of whisker silicon, at high temperature, aluminum hydroxide is transformed into alumina, and alumina can reduce the thermal expansion coefficient of the glass, thereby achieving the effect of temperature change resistance.

[0197] Test Example 5:

[0198] Anti-fouling test:

[0199] Test method: Cut the temperature change resistant glass prepared in each example and comparative example into specimens with a length of 10 cm and a width of 5 cm, and after performing a 10-minute continuous droplet rolling test (45% glycerol) and a mud pouring (45 wt% mud) test, measure the droplet contact angle and the mud contact angle. The results are shown in Table 5.

[0200] Table 5

[0201] Droplet contact angle Mud contact angle Example 1 159.4° 151.3° Example 2 159.8° 151.7° Example 3 158.9° 151.6° Comparative example 1 159.3° 150.9° Comparative example 2 159.1° 151.0° Comparative example 3 159.6° 151.4° Comparative example 4 159.6° 151.8° Comparative example 5 83.8° 79.2° Comparative example 6 159.2° 151.3° Comparative example 7 159.5° 151.1°

[0202] From the comparison of the experimental data in Table 5, it can be found that the temperature change resistant glass material prepared by the present invention has good anti-fouling ability.

[0203] From the comparison of the experimental data of Examples 1, 2, and 3 and Comparative Example 5 in Table 5, it can be found that the droplet contact angles and mud contact angles of Examples 1, 2, and 3 are larger than those of Comparative Example 5, indicating that fluorine atoms have extremely strong electronegativity, making the bond energy of the carbon-fluorine bond relatively large and the surface tension extremely low, enabling the modified polyurea to form a dense protective film on the material surface, thereby preventing the penetration of water, oil, and stains and achieving the anti-fouling effect.

[0204] The specific embodiments described above further elaborate on the purpose, technical solutions, and beneficial effects of the present invention. It should be understood that the above description is only the specific embodiments of the present invention and is not used to limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims

1. A glass material resistant to temperature change, characterized in that, The glass material resistant to temperature change is prepared by mixing modified polyurea and functionalized alumina to obtain a coating material, spraying it on the glass surface, and drying it. The functionalized alumina is prepared by reacting alumina with 3-aminopropyltrimethoxysilane, 4-bromo-2-hydroxybenzaldehyde, and 4-aminopyridine in sequence. The glass is prepared by soaking whisker silicon in an aluminum hydroxide solution, then heating and mixing it with nano-silica, lithium oxide, sodium carbonate, and titanium dioxide, and annealing it. The modified polyurea is prepared by reacting polyaspartic acid ester resin F420, polyaspartic acid ester resin F524, hexamethylene diisocyanate-based polyisocyanate trimer, functional monomer, and capping agent. The functional monomer is prepared by reacting 2,2'-bis(trifluoromethyl)diaminobiphenyl and diethyl maleate. The capping agent is prepared by reacting 4',4”(5”)-diaminodibenzo-15-crown-5 and diethyl maleate.

2. A preparation method of a glass material resistant to temperature change, characterized in that, The preparation method of the glass material resistant to temperature change mainly includes the following preparation steps: (1) Take 20 - 30 parts of whisker silicon, 40 - 50 parts of nano-silica, 2 - 4 parts of lithium oxide, 2 - 3 parts of sodium carbonate, and 4 - 5 parts of titanium dioxide by mass. Soak the whisker silicon in an aluminum hydroxide solution for 2 - 3 min, take it out, add nano-silica, lithium oxide, sodium carbonate, and titanium dioxide, keep it at 1600 - 1700 °C for 2 - 4 h to obtain glass liquid. Pour the glass liquid onto a graphite heating plate to make a plate, transfer it to an annealing furnace at 500 - 600 °C for annealing for 100 - 140 min, and naturally cool it to room temperature to obtain the glass. (2) Mix alumina, ethanol solution, and 3-aminopropyltrimethoxysilane according to a mass ratio of 1:80 - 100:0.3 - 0.5, ultrasonicate for 25 - 35 min, stir at 50 - 70 °C and 200 - 300 r / min for 22 - 26 h, filter, wash with ethanol 3 - 5 times, and dry to obtain pre-modified alumina. Mix the pre-modified alumina and acetonitrile according to a mass ratio of 1:10 - 12, add 4-bromo-2-hydroxybenzaldehyde in an equimolar amount of 3-aminopropyltrimethoxysilane, stir at 200 - 300 r / min for 14 - 18 h, filter, wash with ethanol 3 - 5 times, and dry to obtain modified alumina. Mix the modified alumina, 4-aminopyridine, and acetone according to a mass ratio of 1:0.1 - 0.2:8 - 10, stir at 50 - 60 °C and 200 - 300 r / min for 11 - 13 h, filter, wash with acetone 3 - 5 times, and dry to obtain functionalized alumina. (3) Mix 2,2'-bis(trifluoromethyl)diaminobiphenyl and methanol according to a mass ratio of 1:5 - 7, stir at 200 - 300 r / min under nitrogen protection for 10 - 20 min, raise the temperature to 50 - 55 °C, add diethyl maleate in a molar amount 2 times that of 2,2'-bis(trifluoromethyl)diaminobiphenyl uniformly within 8 - 10 min, raise the temperature to 75 - 85 °C, continue to stir for 34 - 36 h, and dry at 50 - 60 °C for 22 - 24 h to obtain the functional monomer. (4) Mix 4',4”(5”)-diaminodibenzo-15-crown-5 and methanol at a mass ratio of 1:5 - 7, stir at 200 - 300 r / min under nitrogen protection for 10 - 20 min, heat up to 50 - 55 °C, and uniformly add diethyl maleate in an equimolar amount to 4',4”(5”)-diaminodibenzo-15-crown-5 within 8 - 10 min. Then heat up to 75 - 85 °C and continue stirring for 34 - 36 h. Dry at 50 - 60 °C for 22 - 24 h to obtain a capping agent; (5) Mix the functional monomer, capping agent, and tetrahydrofuran evenly at a molar ratio of 3 - 5:1:8 - 10 to obtain a mixed solution. Mix polyaspartate ester resin F420, polyaspartate ester resin F524, hexamethylene diisocyanate-based polyisocyanate trimer, and tetrahydrofuran at a molar ratio of 1:1:1.8 - 2:8 - 10, stir at 50 - 70 °C and 200 - 300 r / min for 50 - 70 min, cool down to 40 - 60 °C, continue stirring, and uniformly add the mixed solution in an amount 3 - 4 times the molar amount of polyaspartate ester resin F420 within 8 - 10 min. Then cool down to 30 - 50 °C and continue stirring for 2 - 4 h to obtain a modified polyurea; (6) Mix the modified polyurea and functionalized alumina at a mass ratio of 1:0.15 - 0.25, stir at 30 - 50 °C and 200 - 300 r / min for 4 - 6 min to obtain a coating material. Spray it on the glass surface, vacuum dry at 50 - 70 °C for 70 - 74 h, and let it stand at room temperature for 70 - 74 h to obtain a temperature-resistant glass.

3. The preparation method of a temperature-resistant glass material according to claim 2, characterized in that, The length of the whisker silicon described in step (1) is 1 - 5 μm.

4. The preparation method of a temperature-resistant glass material according to claim 2, characterized in that, The aluminum hydroxide solution described in step (1) is prepared by mixing aluminum hydroxide and water evenly at a mass ratio of 1:3 - 5.

5. The preparation method of a temperature-resistant glass material according to claim 2, characterized in that The thickness of the board described in step (1) is 18 - 22 mm.

6. The preparation method of a temperature-resistant glass material according to claim 2, characterized in that The ethanol solution described in step (2) is prepared by mixing ethanol and water evenly at a mass ratio of 1:

1.

7. The preparation method of a temperature-resistant glass material according to claim 2, characterized in that, The specific operation of drying described in step (2) is vacuum drying at -10 - 0 °C for 22 - 26 h.

8. The preparation method of a temperature-resistant glass material according to claim 2, characterized in that, The spraying thickness of the coating material described in step (6) is 2 mm.