Surface modification method of hollow glass microspheres, modified hollow glass microspheres and masterbatch

Abstract

The present invention relates to a surface modification method of hollow glass microspheres, modified hollow glass microspheres and masterbatch, belonging to the field of treatment of inorganic materials. The surface modification method of the present invention comprises the following steps: reacting hollow glass microspheres with diisocyanate under the action of a catalyst to carry out a reaction of hydroxyl group and isocyanate group to form urethane group, thereby forming pre-modified hollow glass microspheres; reacting the pre-modified hollow glass microspheres with compound A under the action of a catalyst to carry out a reaction of hydroxyl group and isocyanate group to form urethane group; compound A is CH2=C(CH3)COOR1OH, wherein R1 is a C1-C10 alkylene group. The surface modification method of the present invention increases a layer of polyurethane acrylate elastomer material on the surface of the hollow glass microspheres, improves the compatibility and toughening effect of the hollow glass microspheres, so as to meet the requirements of the mechanical properties of the material while satisfying the lightweight and improving the dimensional stability of the material.

Description

Technical Field

[0001] The present invention relates to a surface modification method for hollow glass microspheres and a masterbatch for household appliance shells, belonging to the field of inorganic material treatment. Background Art

[0002] Plastics have the advantages of light weight, high specific strength, non-corrosion, good insulation, good processability, low processing cost, and suitability for mass production, and play a very important role in the application of household appliances. Most of the plastics used in household appliance shells are thermoplastic plastics, accounting for more than 90%. Among them, acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate (PC), polypropylene (PP), and polystyrene (PS) are the most widely used plastic varieties.

[0003] Since the current household appliance shell materials are all high-molecular materials with a density greater than 1 g / cm 3 ³, and in the production and preparation process, in order to ensure the strength of the material and reduce the cost, it is also necessary to add high-density fillers such as glass fibers and calcium carbonate with a larger density, resulting in the common problems of relatively large weight and insufficient dimensional stability in the current household appliance shells (PC, ABS). Replacing glass fibers, calcium carbonate, etc. with hollow glass microspheres can solve the above problems. However, the addition of hollow glass microspheres will also bring new problems to the material, such as a significant reduction in the impact strength of the material, making the material brittle and easily broken under external force. There is no good solution to the problem that it cannot meet the material usage requirements. Currently, the main method is to improve the brittleness of the material by increasing the dosage of plasticizer in the system or adding elastomers to the system. The extensive use of such substances will lead to the loss of other mechanical properties of the material. At the same time, the extensive use of plasticizer will cause certain harm to the human body. The reason for the brittleness of the material is that the particle size of hollow glass microspheres is larger than that of other fillers (such as calcium carbonate and glass fibers), and the compatibility with the system is poor, and the specific surface area is relatively large, which will absorb the plasticizer in the system. Currently, there is no good way to solve the problems of reduced impact toughness and large brittleness in the use of hollow glass microspheres in household appliance shell materials. Summary of the Invention

[0004] The purpose of the present invention is to provide a surface modification method for hollow glass microspheres to solve the problems of reduced impact toughness and large brittleness in the use of household appliance shell materials using hollow glass microspheres.

[0005] The purpose of the present invention also lies in providing surface-modified hollow glass microspheres obtained by the above surface modification method and a masterbatch for household appliance shells using the surface-modified hollow glass microspheres.

[0006] In order to achieve the above purposes, the technical solution adopted by the surface modification method for hollow glass microspheres of the present invention is:

[0007] A surface modification method for hollow glass microspheres, comprising the following steps:

[0008] 1) Reacting hollow glass microspheres and diisocyanate in an organic solvent under the action of a catalyst to form a urethane group from a hydroxyl group and an isocyanate group, thereby forming pre-modified hollow glass microspheres;

[0009] 2) Reacting the pre-modified hollow glass microspheres with compound A in an organic solvent under the action of a catalyst to form a urethane group from a hydroxyl group and an isocyanate group; compound A is CH2=C(CH3)COOR1OH, where R1 is a C1-C10 alkylene group.

[0010] In the surface modification method for hollow glass microspheres of the present invention, by adding a layer of polyurethane acrylate elastomer material on the surface of the hollow glass microspheres, since the polyurethane acrylate elastomer material has better interfacial compatibility as a polymer material with polymer materials, the compatibility between the surface-modified hollow glass microspheres and the masterbatch system of the home appliance shell can be improved. Moreover, by utilizing the elasticity of the polyurethane acrylate on the surface of the hollow glass microspheres, the surface-modified hollow glass microspheres can have a good toughening effect, so that the impact strength of the home appliance shell material will not be reduced, and while meeting the requirements of lightweight and improving the dimensional stability of the material, the mechanical properties meet the usage requirements of the material.

[0011] The diisocyanate can be one or any combination of aliphatic diisocyanates, cycloaliphatic diisocyanates, and aromatic diisocyanates. Since the polyurethane formed by the reaction of diisocyanate and hydroxyl group has high elasticity, the toughness of the modified hollow glass microspheres can be improved. Due to the uncertainty of the hydroxyl group content on the surface of the hollow glass microspheres, in order to enable the diisocyanate to fully react with the hydroxyl groups on the surface of the hollow glass microspheres, further, the mass ratio of the diisocyanate to the hollow glass microspheres is (10-30):100. The diisocyanate is preferably one or any combination of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and 1,6-hexane diisocyanate.

[0012] In order to fully block the -NCO of the diisocyanate connected to the surface of the hollow glass microspheres, further, in step 2), the molar ratio of the hydroxyl group (-OH) in compound A to the isocyanate group (-NCO) in the diisocyanate is ≥1:1. For example, when the mass ratio of the diisocyanate to the hollow glass microspheres is (10-30):100, the molar ratio of the hydroxyl group in compound A to the isocyanate group in the diisocyanate is 1:1.

[0013] Compound A is reacted with pretreated hollow glass microspheres to block the polyurethane prepolymer on the modified hollow glass microspheres using the hydroxyl groups of Compound A, preventing the microspheres from absorbing water again after drying, and at the same time growing the polymer chain segments on the surface of the hollow glass microspheres, which helps to improve the compatibility between the hollow glass microspheres and the plastic masterbatch. Further, Compound A is hydroxyalkyl methacrylate; the hydroxyalkyl methacrylate is hydroxyethyl methacrylate.

[0014] Further, in step 1), the temperature of the reaction is 70-90 °C, the reaction time is 2-3 h, and the reaction is carried out under vacuum conditions. In step 1), the catalyst used is dibutyltin dilaurate (DBTDL), and the organic solvent used is preferably anhydrous toluene. The dosage of the catalyst is 0.5-1.3% of the mass of the hollow glass microspheres, for example, 0.55% or 0.9%.

[0015] Further, in step 2), the temperature of the reaction is 40-50 °C, the reaction time is 2-3 h, and the reaction is carried out under vacuum conditions. In step 2), the catalyst used is dibutyltin dilaurate (DBTDL), and the organic solvent used is preferably anhydrous toluene.

[0016] Further, in step 2), Compound A and the inhibitor are added to the reaction system containing the pre-modified hollow glass microspheres obtained after the reaction in step 1) to carry out the reaction described in step 2). Directly adding Compound A and the inhibitor to the reaction system containing the pre-modified hollow glass microspheres obtained after the reaction in step 1) to directly carry out the reaction can simplify the production process, and there is no need to re-add the organic solvent and the catalyst, making full use of the organic solvent and the catalyst used in the reaction in step 1), and reducing the production cost.

[0017] The inhibitor can prevent the explosive polymerization of hydroxyethyl methacrylate in the reaction. Further, the addition amount of the inhibitor is 0.5-1.5% of the total mass of the diisocyanate and hydroxyethyl methacrylate, for example, 1%. The inhibitor is preferably hydroquinone (HQ).

[0018] Further, the surface modification method of the hollow glass microspheres further includes the following steps: after the reaction in step 2) is completed, solid-liquid separation is carried out, and the obtained solid is washed and dried. The washing liquid used for washing is an alcohol solvent, for example, ethanol. The drying is vacuum drying, the temperature is 50-60 °C, and the time is 20-30 h.

[0019] The technical solution adopted for the surface-modified hollow glass microspheres of the present invention is:

[0020] A surface-modified hollow glass microsphere obtained by the surface modification method of the above-mentioned hollow glass microsphere.

[0021] The surface-modified hollow glass microspheres of the present invention are obtained by modifying using the above method. When used in the masterbatch for home appliance shells (such as PC or ABS masterbatch), they not only have high compatibility, but also can avoid a significant decrease in the impact strength of the home appliance shell caused by the addition of hollow glass microspheres. The surface-modified hollow glass microspheres of the present invention can enable the hollow glass microspheres to be used in large amounts in the PC / ABS home appliance shell masterbatch while meeting the requirements of impact strength.

[0022] The technical solution adopted by the masterbatch for home appliance shells of the present invention:

[0023] A masterbatch for home appliance shells is composed of the following components in parts by weight: 60 - 80 parts of carrier resin, 15 - 30 parts of the above surface-modified hollow glass microspheres, 0.5 - 1 part of lubricant, and 1 - 2 parts of antioxidant.

[0024] For the masterbatch for home appliance shells of the present invention, using the surface-modified hollow glass microspheres of the present invention as a filler, while having high impact strength, it avoids the use of a large amount of plasticizers and other elastomeric toughening materials. Furthermore, while reducing the harm of plasticizers to the human body, it ensures that other mechanical properties of the material are not lost.

[0025] Further, the carrier resin is one or any combination of acrylonitrile-butadiene-styrene copolymer (ABS resin) and polycarbonate (PC resin).

[0026] It can be understood that the commonly used carrier resin particles, lubricants, and antioxidants for plastic masterbatches can all be used in the masterbatch for home appliance shells of the present invention. Further, the formulated amounts of carrier resin particles, lubricant, and antioxidant are mixed evenly and then added into a twin-screw extruder, and then the surface-modified hollow glass microspheres are added through side feeding, and then pelletized by extrusion. The temperature of the extruder is 230 - 290 °C. Specific embodiments

[0027] The technical solution of the present invention will be further described below in conjunction with specific embodiments.

[0028] The particle size D90 of the hollow glass microspheres used in the following examples and comparative examples is 65 μm, the density is 0.58 - 0.6 g / cm 3 , the wall thickness is 1 - 2 μm, the pH is about 8, and the compressive strength is 12000 psi.

[0029] Example 1

[0030] The surface modification method of the hollow glass microspheres in this example includes the following steps:

[0031] 100 g of vacuum-dried hollow glass microspheres (HGMS) and 200 mL of anhydrous toluene were added to a four-necked flask equipped with mechanical stirring. Under a nitrogen atmosphere, 10 g of isophorone diisocyanate (IPDI) and 0.55 g of dibutyltin dilaurate (DBTDL) as a catalyst were added. After the addition, the system was evacuated, and the reaction was carried out at 80 °C for 4.5 h. Then, the vacuum equipment was turned off and nitrogen was re-introduced. 11.84 g of 2-hydroxyethyl methacrylate (HEMA) and 0.1 g of hydroquinone (HQ) as an inhibitor were added dropwise. The system was evacuated again, and the reaction was carried out at 45 °C for 2.5 h. After the reaction, centrifugation was performed to remove the solvent and excess monomers. Then, the microspheres were washed three times with ethanol and dried in a vacuum drying oven at 55 °C for 24 h to obtain surface-modified hollow glass microspheres.

[0032] Example 2

[0033] The method for surface modification of the hollow glass microspheres in this example includes the following steps:

[0034] 100 g of vacuum-dried hollow glass microspheres (HGMS) and 200 mL of anhydrous toluene were added to a four-necked flask equipped with mechanical stirring. Under a nitrogen atmosphere, 15 g of isophorone diisocyanate (IPDI) and 0.9 g of dibutyltin dilaurate (DBTDL) as a catalyst were added. After the addition, the system was evacuated, and the reaction was carried out at 70 °C for 5 h. Then, the vacuum equipment was turned off and nitrogen was re-introduced. 17.57 g of 2-hydroxyethyl methacrylate (HEMA) and 0.3 g of hydroquinone (HQ) as an inhibitor were added dropwise. The system was evacuated again, and the reaction was carried out at 50 °C for 2 h. After the reaction, centrifugation was performed to remove the solvent and excess monomers. Then, the microspheres were washed twice with ethanol and dried in a vacuum drying oven at 50 °C for 24 h to obtain surface-modified hollow glass microspheres.

[0035] Example 3

[0036] The method for surface modification of the hollow glass microspheres in this example includes the following steps:

[0037] 100 g of vacuum-dried hollow glass microspheres (HGMS) and 200 mL of anhydrous toluene were added to a four-necked flask equipped with mechanical stirring. Under a nitrogen atmosphere, 30 g of isophorone diisocyanate (IPDI) and 1.3 g of dibutyltin dilaurate (DBTDL) as a catalyst were added. After the addition, the system was evacuated, and the reaction was carried out at 90 °C for 4 h. Then, the vacuum equipment was turned off and nitrogen was re-introduced. 35.14 g of 2-hydroxyethyl methacrylate (HEMA) and 0.9 g of hydroquinone (HQ) as an inhibitor were added dropwise. The system was evacuated again, and the reaction was carried out at 40 °C for 3 h. After the reaction, centrifugation was performed to remove the solvent and excess monomers. Then, the microspheres were washed three times with ethanol and dried in a vacuum drying oven at 60 °C for 24 h to obtain surface-modified hollow glass microspheres.

[0038] Example 4

[0039] The surface modification method of the hollow glass microspheres in this example includes the following steps:

[0040] Add 100 g of vacuum-dried hollow glass microspheres (HGMS) and 200 mL of anhydrous toluene into a four-necked flask with mechanical stirring. Under a nitrogen atmosphere, add 15 g of 1,6-hexamethylene diisocyanate and 0.9 g of the catalyst dibutyltin dilaurate (DBTDL). After feeding, evacuate the system, react at 90 °C for 4 hours, then close the vacuum equipment and re-introduce nitrogen. Dropwise add 23.21 g of 2-hydroxyethyl methacrylate (HEMA) and 0.9 g of the inhibitor hydroquinone (HQ). Evacuate the system and react at 40 °C for 3 hours. After the reaction, perform centrifugation to remove the solvent and excess monomer. Then wash the microspheres with ethanol 3 times and dry them in a vacuum drying oven at 60 °C for 24 hours to obtain surface-modified hollow glass microspheres.

[0041] The surface modification principles of the above Examples 1 to 3 are as follows:

[0042]

[0043] Example 5

[0044] The surface-modified glass microspheres in this example are prepared by the modification methods in the above Examples 1 to 4, which will not be elaborated here.

[0045] The lubricant used in the following Examples 6 to 11 and Comparative Examples 1 to 6 is Kao EB-FF from Japan, and the antioxidant is BASF IRGANOX1010.

[0046] Example 6

[0047] The masterbatch for home appliance shells in this example is composed of the following components by weight: 60 parts of ABS resin, 0.5 part of lubricant, 1 part of antioxidant, and 15 parts of surface-modified hollow glass microspheres; the surface-modified hollow glass microspheres used are obtained by surface-modifying the hollow glass microspheres by the method of Example 1. The masterbatch for home appliance shells in this example is prepared by the following method: Mix the ABS resin particles, lubricant, and antioxidant evenly in a mixer, then add them into a twin-screw extruder, and then add the surface-modified hollow glass microspheres through side feeding, and then extrude and pelletize. The temperature of the extruder is 230 °C.

[0048] Example 7

[0049] The masterbatch for the home appliance shell in this embodiment is composed of the following components in parts by weight: 80 parts of ABS resin, 1 part of lubricant, 2 parts of antioxidant, and 30 parts of surface-modified hollow glass microspheres; the surface-modified hollow glass microspheres used are obtained by surface modification in Example 2. The masterbatch for the home appliance shell in this embodiment is prepared by a method including the following steps: Mix the ABS resin particles, lubricant, and antioxidant evenly in a mixer, then add them into a twin-screw extruder, and then add the surface-modified hollow glass microspheres through side feeding, and then extrude and pelletize. The temperature of the extruder is 230°C.

[0050] Example 8

[0051] The masterbatch for the home appliance shell in this embodiment is composed of the following components in parts by weight: 60 parts of PC resin, 0.5 part of lubricant, 1 part of antioxidant, and 15 parts of surface-modified hollow glass microspheres; the surface-modified hollow glass microspheres used are obtained by surface-modifying the hollow glass microspheres by the method in Example 3. The masterbatch for the home appliance shell in this embodiment is prepared by a method including the following steps: Mix the PC resin particles, lubricant, and antioxidant evenly in a mixer, then add them into a twin-screw extruder, and then add the surface-modified hollow glass microspheres through side feeding, and then extrude and pelletize. The temperature of the extruder is 290°C.

[0052] Example 9

[0053] The masterbatch for the home appliance shell in this embodiment is composed of the following components in parts by weight: 80 parts of PC resin, 1 part of lubricant, 2 parts of antioxidant, and 30 parts of surface-modified hollow glass microspheres; the surface-modified hollow glass microspheres used are obtained by surface modification in Example 2. The masterbatch for the home appliance shell in this embodiment is prepared by a method including the following steps: Mix the PC resin particles, lubricant, and antioxidant evenly in a mixer, then add them into a twin-screw extruder, and then add the surface-modified hollow glass microspheres through side feeding, and then extrude and pelletize. The temperature of the extruder is 290°C.

[0054] Example 10

[0055] The masterbatch for the home appliance shell in this embodiment is composed of the following components in parts by weight: 80 parts of ABS resin, 1 part of lubricant, 2 parts of antioxidant, and 30 parts of surface-modified hollow glass microspheres; the surface-modified hollow glass microspheres used are obtained by surface modification in Example 4. The masterbatch for the home appliance shell in this embodiment is prepared by a method including the following steps: Mix the ABS resin particles, lubricant, and antioxidant evenly in a mixer, then add them into a twin-screw extruder, and then add the surface-modified hollow glass microspheres through side feeding, and then extrude and pelletize. The temperature of the extruder is 230°C.

[0056] Example 11

[0057] The masterbatch for the household appliance shell of this embodiment is composed of the following components in parts by weight: 80 parts of PC resin, 1 part of lubricant, 2 parts of antioxidant, and 30 parts of surface-modified hollow glass microspheres; the surface-modified hollow glass microspheres used are obtained by surface modification in Example 4. The masterbatch for the household appliance shell of this embodiment is prepared by a method including the following steps: mixing PC resin particles, lubricant, and antioxidant in proportion in a mixer, then adding them into a twin-screw extruder, adding the surface-modified hollow glass microspheres through side feeding, and then extruding and pelletizing. The temperature of the extruder is 290 °C.

[0058] Comparative Example 1

[0059] The preparation method of the masterbatch for the household appliance shell in this comparative example is only different from the preparation method of the masterbatch for the household appliance shell in Example 6 in that: in this comparative example, the surface-modified hollow glass microspheres used in Example 6 are replaced with unmodified hollow glass microspheres.

[0060] Comparative Example 2

[0061] The preparation method of the masterbatch for the household appliance shell in this comparative example is only different from the preparation method of the masterbatch for the household appliance shell in Example 7 in that: in this comparative example, the surface-modified hollow glass microspheres used in Example 7 are replaced with unmodified hollow glass microspheres.

[0062] Comparative Example 3

[0063] The preparation method of the masterbatch for the household appliance shell in this comparative example is only different from the preparation method of the masterbatch for the household appliance shell in Example 8 in that: in this comparative example, the surface-modified hollow glass microspheres used in Example 8 are replaced with KH570-modified hollow glass microspheres. The preparation method of the KH570-modified hollow glass microspheres includes the following steps: adding a mixed solution of 500 mL of deionized water and ethanol into a stirring kettle, then adding 100 g of hollow glass microspheres, adding KH570 with a mass fraction of 1% of the microspheres, stirring and reacting at room temperature for 2 h, then filtering the reacted hollow glass microspheres by suction, washing them 3 - 5 times with absolute ethanol, drying them in an oven at 80 °C for 12 h, and passing them through a 70 μm sieve after drying, thus preparing the KH570-modified hollow glass microspheres.

[0064] Comparative Example 4

[0065] The preparation method of the masterbatch for the household appliance shell in this comparative example is only different from the preparation method of the masterbatch for the household appliance shell in Example 9 in that: in this comparative example, the surface-modified hollow glass microspheres used in Example 9 are replaced with KH570-modified hollow glass microspheres. The KH570-modified hollow glass microspheres used are the same as those in Comparative Example 3.

[0066] Comparative Example 5

[0067] The preparation method of the home appliance housing masterbatch in this comparative example is only different from that of the home appliance housing masterbatch in Example 6 in that: this comparative example omits the surface-modified hollow glass microspheres, but adds the toughening agent MBS, and the mass ratio of the toughening agent MBS, ABS resin, lubricant, and antioxidant is 10:60:0.5:1.

[0068] Comparative Example 6

[0069] The preparation method of the home appliance housing masterbatch in this comparative example is only different from that of the home appliance housing masterbatch in Example 7 in that: this comparative example omits the surface-modified hollow glass microspheres, but adds the toughening agent MBS, and the mass ratio of the toughening agent MBS, ABS resin, lubricant, and antioxidant is 10:80:1:2.

[0070] Experimental Example

[0071] The properties of the home appliance housing masterbatches prepared in Examples 6 to 9 and the comparative examples were tested respectively. The test methods are as follows:

[0072] Notched impact strength: Refer to GB / T 1843-2008;

[0073] Tensile strength: Refer to GB / T 1040.2-2006;

[0074] Dimensional stability: The home appliance housing masterbatch was injection-molded into a 50 cm * 50 cm square test piece. One corner of the test piece was attached to a flat plate, and the distance from the diagonal to the flat plate was measured, which can represent the degree of warping. The larger the distance, the more serious the warping.

[0075] Table 1 Test Results

[0076]

[0077]

[0078] As can be seen from the data in Table 1, regardless of whether the carrier resin in the masterbatch for home appliance shells is ABS or PC, the impact strength decreases significantly after adding hollow glass microspheres. The higher the content of hollow glass microspheres, the lower the impact strength. The addition of hollow glass microspheres solves the problem of material warping, and at the same time, the tensile strength increases slightly. The decrease in impact strength is because hollow glass microspheres are hard materials, and the addition of hollow glass microspheres increases the brittleness of the material, so the impact strength decreases. The surface of the hollow glass microspheres modified by the present invention has a layer of elastic material, which improves the toughness of the material, so the impact strength and tensile strength increase. Since hollow glass microspheres are spherical materials and isotropic, there is no stress shrinkage problem, so the problem of material warping is solved. For the hollow glass microspheres modified by KH570, because the grafting amount on their surface is small, the brittleness problem of the material cannot be improved, so the improvement of the impact strength and tensile strength is not obvious. Although the addition of a toughening agent can improve the impact strength of the material, compared with the modified hollow glass microspheres of the present invention, the effect is not obvious, and at the same time, it cannot improve the problem of material warping.

Claims

1. A surface modification method for hollow glass microspheres, characterized in that: It includes the following steps: 1) React hollow glass microspheres and diisocyanate in an organic solvent under the action of a catalyst. In this reaction, urethane groups are formed by the reaction of the hydroxyl groups on the surface of the hollow glass microspheres with the isocyanate groups of the diisocyanate, forming pre-modified hollow glass microspheres. The mass ratio of the diisocyanate to the hollow glass microspheres is (10~30):100; 2) React the pre-modified hollow glass microspheres with Compound A in an organic solvent under the action of a catalyst to carry out a reaction in which urethane groups are formed by the reaction of hydroxyl groups and isocyanate groups. Compound A is CH2=C(CH3)COOR1OH, where R1 is a C1~C10 alkylene group. The molar ratio of the hydroxyl group in Compound A to the isocyanate group in the diisocyanate is ≥1:

1.

2. The surface modification method of hollow glass microspheres according to claim 1, characterized in that: The diisocyanate is one or any combination of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and 1,6-hexamethylene diisocyanate.

3. The surface modification method of hollow glass microspheres according to claim 1 or 2, characterized in that: Compound A is hydroxyalkyl methacrylate; the hydroxyalkyl methacrylate is hydroxyethyl methacrylate.

4. The surface modification method of hollow glass microspheres according to claim 1 or 2, characterized in that: In step 1), the reaction temperature is 70~90°C, the reaction time is 2~3 h, and the reaction is carried out under vacuum conditions.

5. The surface modification method of hollow glass microspheres according to claim 1 or 2, characterized in that: In step 2), the reaction temperature is 40~50°C, the reaction time is 2~3 h, and the reaction is carried out under vacuum conditions.

6. The surface modification method of hollow glass microspheres according to claim 1 or 2, characterized in that: In step 2), Compound A and an inhibitor are added to the reaction system containing the pre-modified hollow glass microspheres obtained after the reaction in step 1) to carry out the reaction described in step 2).

7. The surface modification method of hollow glass microspheres according to claim 6, characterized in that: It also includes the following steps: After the reaction in step 2) is completed, solid-liquid separation is carried out, and the obtained solid is washed and dried.

8. A surface-modified hollow glass microsphere obtained by the surface modification method of the hollow glass microsphere according to any one of claims 1~7.

9. A masterbatch for the outer shell of household appliances, characterized in that: It is composed of the following components in parts by weight: 60~80 parts of carrier resin, 15~30 parts of the surface-modified hollow glass microsphere according to claim 8, 0.5~1 part of lubricant, and 1~2 parts of antioxidant.

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