A modified hollow glass microsphere composite material for coating thermal insulation fabrics, its preparation method and application

Abstract

This invention provides a modified hollow glass microsphere composite material for coating thermal insulation fabrics, its preparation method, and its application. The method includes the following steps: (1) reacting hollow glass microspheres with an alkaline solution to obtain hydroxylated hollow glass microspheres; (2) reacting the hydroxylated hollow glass microspheres obtained in step (1) with a silane coupling agent solution to obtain silane coupling agent-modified hollow glass microspheres; (3) reacting the silane coupling agent-modified hollow glass microspheres obtained in step (2), resin, and a crosslinking agent to obtain the modified hollow glass microsphere composite material. The modified hollow glass microsphere composite material prepared by this invention not only has good thermal insulation performance but also retains the original advantages of the coating, such as being thin and comfortable.

Description

Technical Field

[0001] This invention belongs to the field of functional composite materials technology, specifically relating to a modified hollow glass microsphere composite material for coating thermal insulation fabrics, its preparation method, and its application. Background Technology

[0002] Currently, existing technologies for improving the thermal insulation performance of fabrics mainly fall into two categories: On the one hand, to improve the thermal insulation performance of fabrics, researchers introduce air into the fabric by increasing the fabric thickness or adding fillers with low thermal conductivity, such as porous materials, to reduce the thermal conductivity of the fabric and improve its thermal insulation performance; on the other hand, researchers add functional materials, such as phase change materials, to create composites that enable the fabric to store and release heat.

[0003] In summary, traditional methods for increasing the thermal insulation properties of fabrics mainly involve increasing the fabric's thickness and density. These methods, by increasing the fiber content, aim to trap more air and reduce heat conduction and convection. However, this makes the fabric bulky and cumbersome, hindering movement and severely impacting its overall aesthetic appeal.

[0004] Therefore, it is necessary to develop a heat-retaining layer that can keep the fabric warm without significantly increasing the thickness of clothing. This layer can improve the warmth retention of fabrics while also being lighter and more comfortable. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a modified hollow glass microsphere composite material for coating thermal insulation fabrics, its preparation method, and its application. The modified hollow glass microsphere composite material prepared by this invention not only possesses excellent thermal insulation properties but also retains the original advantages of the coating, such as its thinness and comfort.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a method for preparing modified hollow glass microsphere composite materials, the method comprising the following steps:

[0008] (1) Hollow glass microspheres and alkaline solution were reacted once to obtain hydroxylated hollow glass microspheres;

[0009] (2) The hydroxylated hollow glass microspheres obtained in step (1) are reacted with the silane coupling agent solution to obtain silane coupling agent modified hollow glass microspheres.

[0010] (3) The surface-grafted silane coupling agent modified hollow glass microspheres obtained in step (2), resin and crosslinking agent are subjected to crosslinking reaction to obtain the modified hollow glass microsphere composite material.

[0011] This invention first grafts hydroxyl groups onto the surface of hollow glass microspheres using an alkaline solution to obtain hydroxylated hollow glass microspheres. Second, it modifies the surface of the hydroxylated hollow glass microspheres with a silane coupling agent using a mixed solution containing a silane coupling agent, resulting in more uniform dispersion of the hollow glass microspheres in the resin. This plays a crucial role in improving the thermal insulation performance of the composite material. Finally, the silane coupling agent-modified hollow glass microspheres are cross-linked with the resin, reducing the mass of the composite material while improving its thermal insulation performance.

[0012] Preferably, the average diameter of the hollow glass microspheres in step (1) is 15-60 μm, for example, it can be 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, etc.

[0013] Preferably, the hollow glass microspheres in step (1) include at least one of S15 type hollow glass microspheres, K25 type hollow glass microspheres or iM16K type hollow glass microspheres, preferably K25 type hollow glass microspheres.

[0014] In this invention, the hollow glass microspheres of the above-mentioned specific types were all purchased from 3M Company.

[0015] Preferably, the alkaline solution in step (1) includes a sodium hydroxide solution.

[0016] Preferably, the concentration of the alkaline solution in step (1) is 0.4 mol / L to 0.8 mol / L, preferably 0.5 mol / L, for example, it can be 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, etc.

[0017] Preferably, the mass and volume ratio of the hollow glass microspheres and the alkaline solution in step (1) is (5-18g):100mL, more preferably 10g:100mL, for example, it can be 5g:100mL, 7g:100mL, 10g:100mL, 12g:100mL, 13g:100mL, 14g:100mL, 15g:100mL, 16g:100mL, 17g:100mL, 18g:100mL, etc.

[0018] In this invention, by adjusting the mass and volume ratio of hollow glass microspheres and alkaline solution, a suitable hydroxylation ratio on the surface of hollow glass microspheres can be obtained. If the volume ratio is too low, the alkaline solution will be excessive, damaging the internal structure of the hollow glass microspheres. Conversely, if the volume ratio is too high, the hydroxylation effect will be poor, affecting the subsequent grafting effect of silane coupling agent.

[0019] Preferably, the temperature of the first reaction in step (1) is 80-90°C, for example, 80°C, 82°C, 85°C, 88°C, 90°C, etc.; the time is 10-18 min, for example, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min, etc.

[0020] Preferably, a cooling process is performed after the reaction in step (1) is completed.

[0021] Preferably, the cooling process in step (1) is performed to room temperature.

[0022] Preferably, the cooling process in step (1) is followed by filtration, washing, and drying.

[0023] Preferably, the washing process uses deionized water.

[0024] Preferably, the temperature of the first drying is 60-75℃, for example, 60℃, 65℃, 70℃, 75℃, etc.; the time is 24h-48h, for example, 24h, 30h, 36h, 48h, etc.; preferably, the temperature is 70℃ and the time is 24h.

[0025] Preferably, the silane coupling agent solution in step (2) comprises ethanol, water and silane coupling agent.

[0026] Preferably, the water comprises deionized water.

[0027] Preferably, the silane coupling agent includes KH550 and / or KH590, with KH550 being the most preferred.

[0028] Preferably, the volume ratio of ethanol, water and silane coupling agent is (90-95):(5-10):(1-5), preferably 95:5:2, and for example, it can be 90:5:1, 92:6:2, 93:7:3, 94:8:4, 95:5:2, or 95:10:5.

[0029] In this invention, by adjusting the volume ratio of ethanol, deionized water and silane coupling agent, an appropriate amount of silane coupling agent is grafted onto the surface of hollow glass microspheres. If the proportion of silane coupling agent is too low, the grafting effect on the surface of hollow glass microspheres will be poor, affecting its dispersibility in the resin. Conversely, if the proportion is too high, it will result in material waste.

[0030] Preferably, the temperature of the secondary reaction in step (2) is 80℃~90℃, for example, 80℃, 82℃, 85℃, 88℃, 90℃, etc.; the time is 50min~70min, for example, 50min, 55min, 60min, 65min, 70min, etc.

[0031] In this invention, the surface modification effect of hollow glass microspheres is optimized by controlling the time of the secondary reaction.

[0032] Preferably, after the secondary reaction in step (2) is completed, a secondary cooling process is also included.

[0033] Preferably, the secondary cooling process in step (2) is performed to room temperature.

[0034] Preferably, the secondary cooling process in step (2) further includes filtration, washing, and secondary drying processes in sequence.

[0035] Preferably, the washing is performed using an alcohol solvent.

[0036] Preferably, the temperature of the secondary drying is 60-75℃, for example, 60℃, 65℃, 70℃, 75℃, etc.; the time is 24h-48h, for example, 24h, 30h, 36h, 48h, etc.; preferably, the temperature is 70℃ and the time is 24h.

[0037] Preferably, the resin in step (3) includes acrylic resin and / or polyamide resin.

[0038] Preferably, the resin in step (3) includes at least one of L57 type acrylic emulsion, 1500C-3 type resin or 3711C type nylon transparent paste, preferably L57 type acrylic emulsion.

[0039] In this invention, all of the above-mentioned specific types of resins were purchased from Changlian Technology Co., Ltd.

[0040] Preferably, the crosslinking agent includes aziridine crosslinking agents.

[0041] Preferably, the aziridine crosslinking agent is PC-100 (purchased from Changlian Technology Co., Ltd.).

[0042] Preferably, the volume ratio of the surface-grafted silane coupling agent modified hollow glass microspheres to the resin in step (3) is (1-5):(5-9), for example, it can be 1:9, 2:8, 3:7, 4:6, or 5:5.

[0043] In this invention, by adjusting the volume ratio of surface-grafted silane coupling agent-modified hollow glass microspheres to resin, the composite material is kept to have a certain degree of fluidity while achieving the best heat preservation effect. If the ratio is too low, it will affect the heat preservation effect of the composite material, and if it is too high, it will reduce the fluidity of the composite material and affect its application.

[0044] Preferably, the mass ratio of the crosslinking agent to the resin in step (3) is (1-5):(95-99), preferably 2:98, and for example, it can be 1:99, 2:98, 3:97, 4:96, or 5:95.

[0045] In this invention, the crosslinking effect is optimized by adjusting the mass ratio of the crosslinking agent to the resin. If the ratio is too low, the crosslinking time will increase, and if it is too high, raw materials will be wasted.

[0046] Preferably, the temperature of the crosslinking reaction in step (3) is 15 to 30°C, for example, 15°C, 20°C, 25°C, 30°C, etc.; the time is 4 to 6 hours, for example, 4 hours, 5 hours, 6 hours, etc.; preferably, the temperature is 25°C and the time is 6 hours.

[0047] In a second aspect, the present invention provides a modified hollow glass microsphere composite material, which is prepared by the method for preparing modified hollow glass microsphere composite material according to the first aspect.

[0048] Thirdly, the present invention provides a thermal insulation and heat storage coating, the thermal insulation and heat storage coating comprising the modified hollow glass microsphere composite material according to the second aspect.

[0049] Fourthly, the present invention provides a fabric comprising the heat-insulating and heat-storing coating according to the third aspect.

[0050] Compared with the prior art, the present invention has the following beneficial effects:

[0051] This invention provides a method for preparing modified hollow glass microsphere composite materials. First, hydroxyl groups are grafted onto the surface of hollow glass microspheres using an alkaline solution to obtain hydroxylated hollow glass microspheres. Second, the hydroxylated hollow glass microspheres are further modified by surface grafting with a silane coupling agent using a mixed solution containing a silane coupling agent, resulting in more uniform dispersion of the hollow glass microspheres in the resin. This plays a crucial role in improving the thermal insulation performance of the composite material. Finally, the silane coupling agent-modified hollow glass microspheres are cross-linked with the resin, reducing the mass of the composite material while improving its thermal insulation performance. Detailed Implementation

[0052] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0053] In this embodiment, all hollow glass microspheres were purchased from 3M, all resins and crosslinking agents were purchased from Changlian Technology Co., Ltd., and all reagents or instruments used without a specified manufacturer were commercially available products.

[0054] Example 1

[0055] This embodiment provides a modified hollow glass microsphere composite material and its preparation method, the method comprising the following steps:

[0056] (1) 10g of iM16K hollow glass microspheres (average particle size of 20μm) and 100mL of sodium hydroxide solution with a concentration of 0.5mol / L were stirred in a water bath at 90℃ for 15min, cooled to room temperature, filtered and washed 3 times with deionized water, and then dried in a constant temperature drying oven at 70℃ for 24h to obtain hydroxylated hollow glass microspheres.

[0057] (2) Stir 95 mL of ethanol, 5 mL of deionized water and 2 mL of KH550 silane coupling agent evenly and let stand for 10 min to obtain silane coupling agent solution; stir the hydroxylated hollow glass microspheres and silane coupling agent solution obtained in step (1) in a water bath at 85 °C for 1 h, condense and reflux to obtain turbid liquid, cool the turbid liquid to room temperature, filter and wash with ethanol 3 times, and then put it in a constant temperature drying oven at 70 °C for 24 h to obtain hollow glass microspheres modified with surface grafted silane coupling agent;

[0058] (3) The 0.5 mL surface-grafted silane coupling agent modified hollow glass microspheres obtained in step (2), 4.5 mL L57 type acrylic emulsion resin and PC-100 type aziridine crosslinking agent were subjected to a crosslinking reaction at 25 °C for 6 h, wherein the mass ratio of PC-100 type aziridine crosslinking agent to L57 type acrylic emulsion resin was 2:98, to obtain the modified hollow glass microsphere composite material.

[0059] Example 2

[0060] This embodiment provides a modified hollow glass microsphere composite material and its preparation method, the method comprising the following steps:

[0061] (1) 10g of iM16K hollow glass microspheres (average particle size of 20μm) and 100mL of sodium hydroxide solution with a concentration of 0.5mol / L were stirred in a water bath at 90℃ for 15min, cooled to room temperature, filtered and washed 3 times with deionized water, and then dried in a constant temperature drying oven at 70℃ for 24h to obtain hydroxylated hollow glass microspheres.

[0062] (2) Stir 95 mL of ethanol, 5 mL of deionized water and 2 mL of KH550 silane coupling agent evenly and let stand for 10 min to obtain silane coupling agent solution; stir the hydroxylated hollow glass microspheres and silane coupling agent solution obtained in step (1) in a water bath at 85 °C for 1 h, condense and reflux to obtain turbid liquid, cool the turbid liquid to room temperature, filter and wash with ethanol 3 times, and then put it in a constant temperature drying oven at 70 °C for 24 h to obtain hollow glass microspheres modified with surface grafted silane coupling agent;

[0063] (3) The 1.5 mL of surface-grafted silane coupling agent modified hollow glass microspheres obtained in step (2), 3.5 mL of L57 type acrylic emulsion resin and PC-100 type aziridine crosslinking agent were subjected to a crosslinking reaction at 25℃ for 6 h, wherein the mass ratio of PC-100 type aziridine crosslinking agent to L57 type acrylic emulsion resin was 2:98, to obtain the modified hollow glass microsphere composite material.

[0064] Example 3

[0065] This embodiment provides a modified hollow glass microsphere composite material and its preparation method, the method comprising the following steps:

[0066] (1) 10g of iM16K hollow glass microspheres (average particle size of 20μm) and 100mL of sodium hydroxide solution with a concentration of 0.5mol / L were stirred in a water bath at 90℃ for 15min, cooled to room temperature, filtered and washed 3 times with deionized water, and then dried in a constant temperature drying oven at 70℃ for 24h to obtain hydroxylated hollow glass microspheres.

[0067] (2) Stir 95 mL of ethanol, 5 mL of deionized water and 2 mL of KH550 silane coupling agent evenly and let stand for 10 min to obtain silane coupling agent solution; stir the hydroxylated hollow glass microspheres and silane coupling agent solution obtained in step (1) in a water bath at 85 °C for 1 h, condense and reflux to obtain turbid liquid, cool the turbid liquid to room temperature, filter and wash with ethanol 3 times, and then put it in a constant temperature drying oven at 70 °C for 24 h to obtain hollow glass microspheres modified with surface grafted silane coupling agent;

[0068] (3) The 2.5 mL of surface-grafted silane coupling agent modified hollow glass microspheres obtained in step (2), 2.5 mL of L57 type acrylic emulsion resin and PC-100 type aziridine crosslinking agent were subjected to a crosslinking reaction at 25 °C for 6 h, wherein the mass ratio of PC-100 type aziridine crosslinking agent to L57 type acrylic emulsion resin was 2:98, to obtain the modified hollow glass microsphere composite material.

[0069] Example 4

[0070] This embodiment provides a modified hollow glass microsphere composite material and its preparation method, the method comprising the following steps:

[0071] (1) 10g of S15 hollow glass microspheres (average particle size of 55μm) and 0.5mol / L sodium hydroxide solution (volume of 100mL) were stirred in a water bath at 90℃ for 15min, cooled to room temperature, filtered and washed 3 times with deionized water, and then placed in a constant temperature drying oven at 70℃ for 24h to obtain hydroxylated hollow glass microspheres.

[0072] (2) Stir 95 mL of ethanol, 5 mL of deionized water and 2 mL of KH550 silane coupling agent evenly and let stand for 10 min to obtain silane coupling agent solution; stir the hydroxylated hollow glass microspheres and silane coupling agent solution obtained in step (1) in a water bath at 85 °C for 1 h, condense and reflux to obtain turbid liquid, cool the turbid liquid to room temperature, filter and wash with ethanol 3 times, and then put it in a constant temperature drying oven at 70 °C for 24 h to obtain hollow glass microspheres modified with surface grafted silane coupling agent;

[0073] (3) The 0.5 mL surface-grafted silane coupling agent modified hollow glass microspheres obtained in step (2), 4.5 mL L57 type acrylic emulsion resin and PC-100 type aziridine crosslinking agent were subjected to a crosslinking reaction at 25°C for 6 h, wherein the mass ratio of PC-100 type aziridine crosslinking agent to L57 type acrylic emulsion resin was 2:98, to obtain the modified hollow glass microsphere composite material.

[0074] Example 5

[0075] This embodiment provides a modified hollow glass microsphere composite material and its preparation method, the method comprising the following steps:

[0076] (1) 10g of K25 hollow glass microspheres (average particle size of 55μm) and 0.5mol / L sodium hydroxide solution (volume of 100mL) were stirred in a water bath at 90℃ for 15min, cooled to room temperature, filtered and washed 3 times with deionized water, and then placed in a constant temperature drying oven at 70℃ for 24h to obtain hydroxylated hollow glass microspheres.

[0077] (2) Stir 95 mL of ethanol, 5 mL of deionized water and 2 mL of KH550 silane coupling agent evenly and let stand for 10 min to obtain silane coupling agent solution; stir the hydroxylated hollow glass microspheres and silane coupling agent solution obtained in step (1) in a water bath at 85 °C for 1 h, condense and reflux to obtain turbid liquid, cool the turbid liquid to room temperature, filter and wash with ethanol 3 times, and then put it in a constant temperature drying oven at 70 °C for 24 h to obtain hollow glass microspheres modified with surface grafted silane coupling agent;

[0078] (3) The 0.5 mL surface-grafted silane coupling agent modified hollow glass microspheres obtained in step (2), 4.5 mL L57 type acrylic emulsion resin and PC-100 type aziridine crosslinking agent were subjected to a crosslinking reaction at 25 °C for 6 h, wherein the mass ratio of PC-100 type aziridine crosslinking agent to L57 type acrylic emulsion resin was 2:98, to obtain the modified hollow glass microsphere composite material.

[0079] Example 6

[0080] The difference between this embodiment and embodiment 1 is that the mass and volume ratio of hollow glass microspheres and sodium hydroxide solution in step (1) is 5g:100mL, while all other aspects are the same as in embodiment 1.

[0081] Example 7

[0082] The difference between this embodiment and embodiment 1 is that the mass and volume ratio of hollow glass microspheres and sodium hydroxide solution in step (1) is 20g:100mL, while all other aspects are the same as in embodiment 1.

[0083] Example 8

[0084] The difference between this embodiment and embodiment 1 is that the volume ratio of ethanol, deionized water and silane coupling agent in step (2) is 95:5:1, while all other aspects are the same as in embodiment 1.

[0085] Example 9

[0086] The difference between this embodiment and embodiment 1 is that the volume ratio of ethanol, deionized water and silane coupling agent in step (2) is 95:5:5 for ethanol, while all other aspects are the same as in embodiment 1.

[0087] Example 10

[0088] The difference between this embodiment and embodiment 1 is that the volume ratio of the surface-grafted silane coupling agent modified hollow glass microspheres to the resin in step (3) is 1:24, while all other aspects are the same as in embodiment 1.

[0089] Comparative Example 1

[0090] The difference between this comparative example and Example 1 is that the modification treatment in step (2) is not performed, only the treatment in steps (1) and (3) is performed, and the rest is the same as Example 1.

[0091] Comparative Example 2

[0092] The difference between this comparative example and Example 1 is that the modification treatment in step (1) is not performed, and the hydroxylated hollow glass microspheres in step (2) are replaced with unmodified hollow glass microspheres. Everything else is the same as in Example 1.

[0093] Comparative Example 3

[0094] This comparative example provides an L57 type acrylic emulsion.

[0095] Comparative Example 4

[0096] This comparative example provides a 3711C type nylon transparent paste.

[0097] Test conditions

[0098] The modified hollow glass microsphere composite materials provided in Examples 1 to 10 and Comparative Examples 1 to 4 were tested using the following methods:

[0099] (1) Thermal diffusivity: The materials provided in the examples and comparative examples were slowly dripped into the mold to prepare a thermally conductive disc with a diameter of 12.7 mm and a thickness of 1 mm. After carbon spraying one side of the thermally conductive disc, it was placed in a thermal conductivity meter to measure its thermal diffusivity.

[0100] (2) Specific heat: 12.6 mg of the material provided in the examples and comparative examples was placed in a differential scanning calorimeter and its specific heat at 25°C was measured.

[0101] (3) Density: The materials provided in the examples and comparative examples were slowly dripped into the mold to prepare a heat-conducting disc with a diameter of 12.7 mm and a thickness of 1 mm. The heat-conducting disc was placed in a densitometer and its density was measured by Archimedes' principle.

[0102] (4) Thermal conductivity: The thermal conductivity is obtained by multiplying the thermal diffusivity, specific heat and density.

[0103] The test results are shown in Table 1:

[0104] Table 1

[0105]

[0106]

[0107] As shown in Table 1, the addition of silane coupling agent to the surface-treated hollow glass microspheres of the modified hollow glass microsphere composite material significantly reduced the thermal conductivity, indicating a substantial improvement in thermal insulation performance. When the hollow glass microsphere type was K25 and the addition amount was 10% (by volume), the density of the prepared modified hollow glass microsphere composite material was 85% of that of the raw material, the thermal conductivity decreased by approximately 28%, and a certain degree of fluidity was retained. This further demonstrates that the modified hollow glass microsphere composite material improved thermal insulation performance while reducing material weight.

[0108] Example 7 shows that when the mass-to-volume ratio of hollow glass microspheres to sodium hydroxide solution is too high, the excess sodium hydroxide solution will destroy the hollow structure of the hollow glass microspheres, causing the hollow glass microspheres to lose their function of reducing thermal conductivity and become ordinary glass materials. Therefore, the thermal conductivity is higher than that of existing materials.

[0109] Comparative Examples 1-2 show that the composite materials obtained without hydroxylation treatment or surface grafting with silane coupling agent have high thermal diffusivity and thermal conductivity, which is not conducive to improving the thermal insulation performance of the fabric. Comparative Examples 3-4 show that the heat storage layer prepared by the resin provided by the prior art is heavy and has high thermal conductivity, resulting in poor heat storage capacity.

[0110] The applicant declares that the present invention is illustrated by the above embodiments, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials used in the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing modified hollow glass microsphere composite materials, characterized in that, The method includes the following steps: (1) Hollow glass microspheres and alkaline solution are reacted once to obtain hydroxylated hollow glass microspheres; (2) The hydroxylated hollow glass microspheres obtained in step (1) are subjected to a secondary reaction with the silane coupling agent solution to obtain hollow glass microspheres modified with surface grafted silane coupling agent. (3) The surface-grafted silane coupling agent modified hollow glass microspheres obtained in step (2), resin and crosslinking agent are subjected to crosslinking reaction to obtain the modified hollow glass microsphere composite material; The concentration of the alkaline solution mentioned in step (1) is 0.4 mol / L to 0.8 mol / L; The mass and volume ratio of the hollow glass microspheres and the alkaline solution in step (1) is 10g:100mL; The silane coupling agent solution mentioned in step (2) includes ethanol, water and silane coupling agent; The volume ratio of the ethanol, water and silane coupling agent is (90~95):(5~10):(1~5); The resin mentioned in step (3) includes at least one of L57 type acrylic emulsion, 1500C-3 type resin or 3711C type nylon transparent paste; The temperature of the first reaction in step (1) is 80~90℃ and the time is 10~18min; The volume ratio of the surface-grafted silane coupling agent modified hollow glass microspheres to the resin in step (3) is (1~5):(5~9); The mass ratio of the crosslinking agent to the resin in step (3) is (1~5):(95~99).

2. The method according to claim 1, characterized in that, The average diameter of the hollow glass microspheres mentioned in step (1) is 15-60 μm.

3. The method according to claim 1, characterized in that, The hollow glass microspheres mentioned in step (1) include at least one of the following: S15 type hollow glass microspheres, K25 type hollow glass microspheres, or iM16K type hollow glass microspheres.

4. The method according to claim 3, characterized in that, The hollow glass microspheres mentioned in step (1) are K25 type hollow glass microspheres.

5. The method according to claim 1, characterized in that, The alkaline solution mentioned in step (1) includes sodium hydroxide solution.

6. The method according to claim 1, characterized in that, The concentration of the alkaline solution in step (1) is 0.5 mol / L.

7. The method according to claim 1, characterized in that, After the reaction described in step (1) is completed, a cooling process is performed.

8. The method according to claim 7, characterized in that, The cooling process described in step (1) is brought to room temperature.

9. The method according to claim 7, characterized in that, The cooling process described in step (1) is followed by filtration, washing and drying.

10. The method according to claim 9, characterized in that, The washing process uses deionized water.

11. The method according to claim 9, characterized in that, The drying temperature is 60~75℃ and the time is 24h~48h.

12. The method according to claim 11, characterized in that, The drying process was carried out at a temperature of 70°C for 24 hours.

13. The method according to claim 1, characterized in that, The water includes deionized water.

14. The method according to claim 1, characterized in that, The silane coupling agents include models KH550 and / or KH590.

15. The method according to claim 14, characterized in that, The silane coupling agent is designated as KH550.

16. The method according to claim 1, characterized in that, The volume ratio of the ethanol, water, and silane coupling agent is 95:5:

2.

17. The method according to claim 1, characterized in that, The temperature of the secondary reaction in step (2) is 80℃~90℃ and the time is 50min~70min.

18. The method according to claim 1, characterized in that, After the secondary reaction in step (2) is completed, a secondary cooling process is also included.

19. The method according to claim 18, characterized in that, The secondary cooling process described in step (2) is brought to room temperature.

20. The method according to claim 18, characterized in that, The secondary cooling process described in step (2) further includes filtration, washing, and secondary drying.

21. The method according to claim 20, characterized in that, The washing process uses alcohol-based solvents.

22. The method according to claim 20, characterized in that, The secondary drying temperature is 60~75℃, and the time is 24h~48h.

23. The method according to claim 22, characterized in that, The secondary drying temperature is 70℃ and the time is 24 hours.

24. The method according to claim 1, characterized in that, The resin mentioned in step (3) is L57 type acrylic emulsion.

25. The method according to claim 1, characterized in that, The crosslinking agent includes aziridine crosslinking agents.

26. The method according to claim 25, characterized in that, The aziridine crosslinking agent is model PC-100.

27. The method according to claim 1, characterized in that, The mass ratio of the crosslinking agent to the resin in step (3) is 2:

98.

28. The method according to claim 1, characterized in that, The cross-linking reaction in step (3) is carried out at a temperature of 15~30℃ for 4~6h.

29. The method according to claim 28, characterized in that, The cross-linking reaction in step (3) is carried out at a temperature of 25°C for 6 hours.

30. A modified hollow glass microsphere composite material, characterized in that, The modified hollow glass microsphere composite material is prepared by the method for preparing modified hollow glass microsphere composite material according to any one of claims 1-29.

31. A heat-insulating and heat-storing coating, characterized in that, The heat-insulating and heat-storing coating includes the modified hollow glass microsphere composite material according to claim 30.

32. A fabric, characterized in that, The fabric includes the heat-insulating and heat-retaining material according to claim 31. Thermal coating.

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