Silica particle coated hollow glass bead and rubber composite material thereof

Abstract

The invention provides a silicon dioxide particle coated hollow glass bead and a rubber composite material thereof, and belongs to the technical field of high polymer materials. The hollow glass beads are prepared by the following steps: mixing hollow glass beads and white carbon black according to a mass ratio of 1: (5-20), heating at 400-460 DEG C, and coating the surfaces of the beads with white carbon black particles by high-temperature calcination to obtain the modified hollow glass beads with silicon dioxide particle coating amount of 5-20%. The surface roughness of the modified microbead is increased, and the problem that the interface bonding force between the microbead and a rubber matrix is poor is effectively solved. In addition, the invention also provides the modified hollow glass bead / rubber composite material. While the density of the material is reduced, the shore A hardness, the tensile strength, the elongation at break, the wear resistance and other mechanical properties are remarkably improved. Therefore, the invention provides a simple and effective new way for preparing the low-density and high-performance rubber composite material.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a silicon dioxide particle-coated hollow glass microsphere and a rubber composite material thereof. Background Art

[0002] Hollow glass microspheres are a new type of energy-saving, clean, lightweight filler. Featuring a hollow core, lightweight construction, thermal insulation, and high electrical insulation strength, they are widely used in rubber and plastics, coatings, fiberglass reinforced plastics (FRP), emulsion explosives, and oil drilling. With the rapid development of aviation, aerospace, new high-speed trains, luxury yachts, thermal insulation coatings, and bowling, high-performance hollow glass microspheres are attracting increasing attention in a wide range of fields.

[0003] Hollow glass microspheres can effectively reduce the density of rubber while avoiding the many quality issues associated with complex physical or chemical foaming processes. However, the very smooth surface and large particle size of hollow glass microspheres (20-40 μm) result in poor interfacial interaction with the rubber matrix, which negatively impacts the performance of rubber composites. Furthermore, hollow glass microspheres have low mechanical strength and are prone to breakage when subjected to shear forces during rubber processing. Therefore, surface modification of the hollow glass microspheres is necessary to strengthen the interfacial adhesion between the microspheres and the matrix polymer, thereby improving the mechanical properties of the composite.

[0004] At present, common modification methods for hollow glass microspheres include surface chemical modification and physical modification. Among them, chemical modification refers to changing the surface chemical properties of hollow glass microspheres by using compounds such as silane coupling agents KH550 and KH570. For example, patent CN202411173599.9 uses a silane coupling agent to modify hollow glass microspheres, and applies the modified microspheres to rubber preparation. The density of the rubber products obtained by this method decreases, and the compatibility between the microspheres and the rubber is improved, but the tensile strength is around 2MPa, and the mechanical strength is insufficient. Patent CN202211739091.1 uses a titanate coupling agent to modify hollow glass microspheres, generates titanium dioxide by high-temperature calcination, and wraps it on the surface of the microspheres. The microspheres prepared by this method are highly stable, and the coating thickness can be controlled by using the same process for multiple coatings, but the preparation method is relatively complicated and does not involve application in rubber. Therefore, in order to improve the interface strength between hollow glass microspheres and rubber, it is necessary to prepare hollow glass microspheres with a new surface structure, which can then be further mixed with rubber to prepare a low-density, high-strength rubber material. Summary of the Invention

[0005] The object of the present invention is to provide a silicon dioxide particle-coated hollow glass microsphere and a rubber composite material thereof, thereby preparing a low-density, high-strength rubber material.

[0006] To achieve the above object, the present invention provides the following technical solutions: First, the present invention provides a method for preparing modified hollow glass microspheres coated with silica particles, the method comprising the following steps: (1) Mix hollow glass microspheres and white carbon black in a mass ratio of 1:5-20 and place them in a heating container; (2) Set the muffle furnace temperature to 400-460°C, place the heating container in it, heat it, and then cool it to room temperature to obtain a preliminary sample; (3) Add deionized water to completely immerse the sample, let it stand, and then take the floating components on the upper layer; (4) Drying the upper floating component to obtain modified hollow glass microspheres with a silica particle coating amount of 5-20%.

[0007] Preferably, in step (2), the heating time is 60 min; In the step (3), the standing time is 30 minutes.

[0008] Preferably, the modified hollow glass microspheres are prepared by the above-mentioned preparation method.

[0009] Preferably, the particle size of the modified hollow glass microspheres is 20-40 μm.

[0010] Secondly, the present invention provides a modified hollow glass microsphere / rubber composite material, wherein the modified hollow glass microsphere / rubber composite material includes: a modified hollow glass microsphere / butadiene rubber composite material, a modified hollow glass microsphere / white carbon black / butadiene rubber composite material, and a modified hollow glass microsphere / carbon black / butadiene rubber composite material; The modified hollow glass microspheres are prepared by the above-mentioned preparation method.

[0011] Preferably, the raw materials for preparing the modified hollow glass microsphere / butadiene rubber composite material include, by weight: 100 parts of butadiene rubber, 3 parts of zinc oxide, 2 parts of stearic acid, 10 parts of modified hollow glass microspheres, 1 part of accelerator NS, and 1.5 parts of sulfur.

[0012] Preferably, the raw materials for preparing the modified hollow glass microspheres / white carbon black / butadiene rubber composite material include, by weight: 100 parts of butadiene rubber, 3 parts of zinc oxide, 2 parts of stearic acid, 10 parts of modified hollow glass microspheres, 1 part of accelerator NS, 1.5 parts of sulfur, and 30 parts of white carbon black.

[0013] Preferably, the raw materials for preparing the modified hollow glass microspheres / carbon black / butadiene rubber composite material include, by weight: 100 parts of butadiene rubber, 3 parts of zinc oxide, 2 parts of stearic acid, 10 parts of modified hollow glass microspheres, 1 part of accelerator NS, 1.5 parts of sulfur, and 30 parts of carbon black.

[0014] Preferably, the preparation method of the modified hollow glass microsphere / rubber composite material comprises the following steps: (1) After setting the internal mixer temperature to 80-100 °C and the speed to 40-60 rpm, add the following mixing formula in parts by weight: 100 parts of butadiene rubber, 3 parts of zinc oxide, 2 parts of stearic acid, 10 parts of hollow glass microspheres, 1 part of accelerator NS, 1.5 parts of sulfur, 0-30 parts of white carbon black or carbon black; (2) After mixing evenly, perform debonding at a temperature below 100 °C, then perform tableting and cool for 24 h to obtain a rubber mixture; (3) The rubber mixture is placed in a flat plate vulcanizer at 150° C. for vulcanization to obtain the modified hollow glass microsphere / rubber composite material.

[0015] Finally, the present invention provides a method for preparing a modified hollow glass microsphere / rubber composite material, which comprises the following steps: (1) Set the internal mixer temperature to 80-100°C and the speed to 40-60 rpm, and add the following mixing formula: 100 parts of butadiene rubber, 3 parts of zinc oxide, 2 parts of stearic acid, 10 parts of hollow glass microspheres, 1 part of accelerator NS, 1.5 parts of sulfur, 0-30 parts of white carbon black or carbon black; (2) After mixing evenly, perform debonding at a temperature below 100 °C, then perform tableting and cool for 24 hours to obtain a rubber mix; (3) placing the rubber mixture in a flat vulcanizer at 150° C. for vulcanization to obtain the modified hollow glass microsphere / rubber composite material; The modified hollow glass microspheres are prepared by the above-mentioned preparation method.

[0016] The beneficial effects of the present invention are: The present invention attaches silica particles to the surface of hollow glass microspheres by high-temperature sintering. On the one hand, a core-shell structure is formed, which increases the roughness of the microsphere surface, strengthens the mechanical bite force of the modified hollow glass microspheres, and improves the interface strength with the rubber matrix material. On the other hand, the silica particles are attached to the surface, which improves the surface strength of the hollow glass microspheres, reduces the shear crushing rate, and ensures the mechanical properties and lightweight effect of the rubber matrix material. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 Scanning electron microscope images of the hollow glass microspheres modified by sintering with silica in Comparative Example 1 (a) and Examples 1-4 (be). DETAILED DESCRIPTION

[0018] The technical solutions of the present invention are described in detail below through specific embodiments, but the scope of the present invention is not limited by these embodiments.

[0019] Example 1 Preparation of modified hollow glass microspheres with a silica coating content of 5% (5%-modified hollow glass microspheres) (1) Hollow glass microspheres and white carbon black were mixed evenly in a crucible at a mass ratio of 1:20; (2) The temperature of the muffle furnace was set to 400 °C, the crucible was placed in it, heated for 60 min, and cooled to room temperature to obtain a preliminary sample; (3) Add deionized water to completely immerse the preliminary sample, let it stand for 30 minutes, and then take the floating components on the upper layer; (4) The upper floating component was placed in an oven at 100°C and dried for 6 h to obtain modified hollow glass microspheres with a silica coating of 5%.

[0020] Example 2 Preparation of modified hollow glass microspheres with a silica coating of 10% (10%-modified hollow glass microspheres) (1) Hollow glass microspheres and white carbon black were mixed evenly in a crucible at a mass ratio of 1:10; (2) The temperature of the muffle furnace was set to 420 °C, the crucible was placed in it, heated for 60 min, and cooled to room temperature to obtain a preliminary sample; (3) Add deionized water to completely immerse the preliminary sample, let it stand for 30 minutes, and then take the floating components on the upper layer; (4) The upper floating component was placed in an oven at 100°C and dried for 6 h to obtain modified hollow glass microspheres with a silica coating of 10%.

[0021] Example 3 Preparation of modified hollow glass microspheres with a silica coating of 15% (15%-modified hollow glass microspheres) (1) Hollow glass microspheres and white carbon black were mixed evenly in a crucible at a mass ratio of 3:20; (2) The temperature of the muffle furnace was set to 440 °C, the crucible was placed in it, heated for 60 min, and cooled to room temperature to obtain a preliminary sample; (3) Add deionized water to completely immerse the preliminary sample, let it stand for 30 minutes, and then take the floating components on the upper layer; (4) The upper floating component was placed in an oven at 100°C and dried for 6 h to obtain modified hollow glass microspheres with a silica coating of 15%.

[0022] Example 4 Preparation of modified hollow glass microspheres with a silica coating of 20% (20%-modified hollow glass microspheres) (1) Hollow glass microspheres and white carbon black were mixed evenly in a crucible at a mass ratio of 1:5; (2) The temperature of the muffle furnace was set to 460°C, the crucible was placed in it, heated for 60 minutes, and cooled to room temperature to obtain a preliminary sample; (3) Add deionized water to completely immerse the preliminary sample, let it stand for 30 minutes, and then take the floating components on the upper layer; (4) The upper floating component was placed in an oven at 100°C and dried for 6 h to obtain modified hollow glass microspheres with a silica coating of 20%.

[0023] Example 5 Preparation of 5%-modified hollow glass microspheres / butadiene rubber composites (1) After setting the internal mixer temperature to 80 °C and the speed to 60 rpm, add the following mixing formula: BR 100 parts, zinc oxide 3 parts, stearic acid 2 parts, 5%-modified hollow glass microspheres 10 parts, accelerator NS 1 part, sulfur 1.5 parts; (2) Add the formulated materials according to the standard process, wait until the torque is stable, and then perform the debonding at a temperature below 100 °C. Then, unroll the sheet on the open mill and cool it for 24 h to obtain the mixed rubber. (3) The mixed rubber was placed in a flat vulcanizer at 150°C and vulcanized according to the positive vulcanization time tested by the vulcanizer to obtain a vulcanized rubber (i.e., 5%-modified hollow glass microspheres / butadiene rubber composite material).

[0024] Example 6 Preparation of 10%-modified hollow glass microspheres / butadiene rubber composites (1) After setting the internal mixer temperature to 80 °C and the speed to 60 rpm, add the following mixing formula: BR 100 parts, zinc oxide 3 parts, stearic acid 2 parts, 10%-modified hollow glass microspheres 10 parts, accelerator NS 1 part, sulfur 1.5 parts; (2) Add the formulated materials according to the standard process, wait until the torque is stable, and then perform the debonding at a temperature below 100 °C. Then, unroll the sheet on the open mill and cool it for 24 h to obtain the mixed rubber. (3) The mixed rubber was placed in a flat vulcanizer at 150°C and vulcanized according to the positive vulcanization time tested by the vulcanizer to obtain a vulcanized rubber (i.e., 10%-modified hollow glass microspheres / butadiene rubber composite material).

[0025] Example 7 Preparation of 15%-modified hollow glass microspheres / butadiene rubber composites (1) After setting the internal mixer temperature to 80 °C and the speed to 60 rpm, add the following mixing formula: BR 100 parts, zinc oxide 3 parts, stearic acid 2 parts, 15%-modified hollow glass microspheres 10 parts, accelerator NS 1 part, sulfur 1.5 parts; (2) Add the formulated materials according to the standard process, wait until the torque is stable, and then perform the debonding at a temperature below 100 °C. Then, unroll the sheet on the open mill and cool it for 24 h to obtain the mixed rubber. (3) The mixed rubber was placed in a flat vulcanizer at 150°C and vulcanized according to the positive vulcanization time tested by the vulcanizer to obtain a vulcanized rubber (i.e., 15%-modified hollow glass microspheres / butadiene rubber composite material).

[0026] Example 8 Preparation of 20%-modified hollow glass microspheres / butadiene rubber composites (1) After setting the internal mixer temperature to 80 °C and the speed to 60 rpm, add the following mixing formula: BR 100 parts, zinc oxide 3 parts, stearic acid 2 parts, 20%-modified hollow glass microspheres 10 parts, accelerator NS 1 part, sulfur 1.5 parts; (2) Add the formulated materials according to the standard process, wait until the torque is stable, and then perform the debonding at a temperature below 100 °C. Then, unroll the sheet on the open mill and cool it for 24 h to obtain the mixed rubber. (3) The mixed rubber was placed in a flat vulcanizer at 150°C and vulcanized according to the positive vulcanization time tested by the vulcanizer to obtain a vulcanized rubber (i.e., 20%-modified hollow glass microspheres / butadiene rubber composite material).

[0027] Example 9 Preparation of 5%-modified hollow glass microspheres / silica / butadiene rubber composites (1) Set the internal mixer temperature to 100 °C and the speed to 40 rpm, and add the following mixing formula: BR 100 parts, zinc oxide 3 parts, stearic acid 2 parts, 5%-modified hollow glass microspheres 10 parts, accelerator NS 1 part, sulfur 1.5 parts, white carbon black 30 parts; (2) Add the formulated materials according to the standard process, wait until the torque is stable, and then perform the debonding at a temperature below 100 °C. Then, unroll the sheet on the open mill and cool it for 24 h to obtain the mixed rubber. (3) The rubber mixture was placed in a flat vulcanizer at 150°C and vulcanized according to the positive vulcanization time tested by the vulcanizer to obtain a vulcanized rubber (i.e., 5%-modified hollow glass microspheres / white carbon black / butadiene rubber composite material).

[0028] Example 10 Preparation of 10%-modified hollow glass microspheres / silica / butadiene rubber composites (1) Set the internal mixer temperature to 100 °C and the speed to 40 rpm, and add the following mixing formula: BR 100 parts, zinc oxide 3 parts, stearic acid 2 parts, 10%-modified hollow glass microspheres 10 parts, accelerator NS 1 part, sulfur 1.5 parts, white carbon black 30 parts; (2) Add the formulated materials according to the standard process, wait until the torque is stable, and then perform the debonding at a temperature below 100 °C. Then, unroll the sheet on the open mill and cool it for 24 h to obtain the mixed rubber. (3) The mixed rubber was placed in a flat vulcanizer at 150°C and vulcanized according to the positive vulcanization time tested by the vulcanizer to obtain a vulcanized rubber (i.e., a 10%-modified hollow glass microsphere / white carbon black / butadiene rubber composite material).

[0029] Example 11 Preparation of 15%-modified hollow glass microspheres / silica / butadiene rubber composites (1) Set the internal mixer temperature to 100 °C and the speed to 40 rpm, and add the following mixing formula: BR 100 parts, zinc oxide 3 parts, stearic acid 2 parts, 15%-modified hollow glass microspheres 10 parts, accelerator NS 1 part, sulfur 1.5 parts, white carbon black 30 parts; (2) Add the formulated materials according to the standard process, wait until the torque is stable, and then perform the debonding at a temperature below 100 °C. Then, unroll the sheet on the open mill and cool it for 24 h to obtain the mixed rubber. (3) The mixed rubber was placed in a flat vulcanizer at 150°C and vulcanized according to the positive vulcanization time tested by the vulcanizer to obtain a vulcanized rubber (i.e., a 15%-modified hollow glass microsphere / white carbon black / butadiene rubber composite material).

[0030] Example 12 Preparation of 20%-modified hollow glass microspheres / silica / butadiene rubber composites (1) Set the internal mixer temperature to 100 °C and the speed to 40 rpm, and add the following mixing formula: BR 100 parts, zinc oxide 3 parts, stearic acid 2 parts, 20%-modified hollow glass microspheres 10 parts, accelerator NS 1 part, sulfur 1.5 parts, white carbon black 30 parts; (2) Add the formulated materials according to the standard process, wait until the torque is stable, and then perform the debonding at a temperature below 100 °C. Then, unroll the sheet on the open mill and cool it for 24 h to obtain the mixed rubber. (3) The mixed rubber was placed in a flat vulcanizer at 150°C and vulcanized according to the positive vulcanization time tested by the vulcanizer to obtain a vulcanized rubber (i.e., a 20%-modified hollow glass microsphere / white carbon black / butadiene rubber composite material).

[0031] Example 13 Preparation of 5%-modified hollow glass microspheres / carbon black / butadiene rubber composites (1) Set the internal mixer temperature to 100 °C and the speed to 40 rpm, and add the following mixing formula: BR 100 parts, zinc oxide 3 parts, stearic acid 2 parts, 5%-modified hollow glass microspheres 10 parts, accelerator NS 1 part, sulfur 1.5 parts, carbon black 30 parts; (2) Add the formulated materials according to the standard process, wait until the torque is stable, and then perform the debonding at a temperature below 100 °C. Then, unroll the sheet on the open mill and cool it for 24 h to obtain the mixed rubber. (3) The mixed rubber was placed in a flat vulcanizer at 150°C and vulcanized according to the positive vulcanization time tested by the vulcanizer to obtain a vulcanized rubber (i.e., a 5%-modified hollow glass microsphere / carbon black / butadiene rubber composite material).

[0032] Example 14 Preparation of 10%-modified hollow glass microspheres / carbon black / butadiene rubber composites (1) Set the internal mixer temperature to 100 °C and the speed to 40 rpm, and add the following mixing formula: BR 100 parts, zinc oxide 3 parts, stearic acid 2 parts, 10%-modified hollow glass microspheres 10 parts, accelerator NS 1 part, sulfur 1.5 parts, carbon black 30 parts; (2) Add the formulated materials according to the standard process, wait until the torque is stable, and then perform the debonding at a temperature below 100 °C. Then, unroll the sheet on the open mill and cool it for 24 h to obtain the mixed rubber. (3) The rubber mixture was placed in a flat vulcanizer at 150°C and vulcanized according to the positive vulcanization time tested by the vulcanizer to obtain a vulcanized rubber (i.e., a 10%-modified hollow glass microsphere / carbon black / butadiene rubber composite material).

[0033] Example 15 Preparation of 15%-modified hollow glass microspheres / carbon black / butadiene rubber composites (1) Set the internal mixer temperature to 100 °C and the speed to 40 rpm, and add the following mixing formula: BR 100 parts, zinc oxide 3 parts, stearic acid 2 parts, 15%-modified hollow glass microspheres 10 parts, accelerator NS 1 part, sulfur 1.5 parts, carbon black 30 parts; (2) Add the formulated materials according to the standard process, wait until the torque is stable, and then perform the debonding at a temperature below 100 °C. Then, unroll the sheet on the open mill and cool it for 24 h to obtain the mixed rubber. (3) The rubber mixture was placed in a flat vulcanizer at 150°C and vulcanized according to the positive vulcanization time tested by the vulcanizer to obtain a vulcanized rubber (i.e., a 15%-modified hollow glass microsphere / carbon black / butadiene rubber composite material).

[0034] Example 16 Preparation of 20%-modified hollow glass microspheres / carbon black / butadiene rubber composites (1) Set the internal mixer temperature to 100 °C and the speed to 40 rpm, and add the following mixing formula: BR 100 parts, zinc oxide 3 parts, stearic acid 2 parts, 20%-modified hollow glass microspheres 10 parts, accelerator NS 1 part, sulfur 1.5 parts, carbon black 30 parts; (2) Add the formulated materials according to the standard process, wait until the torque is stable, and then perform the debonding at a temperature below 100 °C. Then, unroll the sheet on the open mill and cool it for 24 h to obtain the mixed rubber. (3) The mixed rubber was placed in a flat vulcanizer at 150°C and vulcanized according to the positive vulcanization time tested by the vulcanizer to obtain a vulcanized rubber (i.e., a 20%-modified hollow glass microsphere / carbon black / butadiene rubber composite material).

[0035] Comparative Example 1 Preparation of hollow glass microspheres / butadiene rubber composites (1) After setting the internal mixer temperature to 80 °C and the speed to 60 rpm, add the following mixing formula: BR 100 parts, zinc oxide 3 parts, stearic acid 2 parts, hollow glass microspheres 10 parts (unmodified), accelerator NS (N-tert-butyl-2-benzothiazole sulfenamide) 1 part, sulfur 1.5 parts; (2) Add the formulated materials according to the standard process, wait until the torque is stable, and then perform the debonding at a temperature below 100 °C. Then, unroll the sheet on the open mill and cool it for 24 h to obtain the mixed rubber. (3) The mixed rubber is placed in a flat vulcanizer at 150°C and vulcanized according to the positive vulcanization time tested by the vulcanizer to obtain a vulcanized rubber (i.e., hollow glass microspheres / butadiene rubber composite material).

[0036] Comparative Example 2 Preparation of hollow glass microspheres / silica / butadiene rubber composites (1) Set the internal mixer temperature to 100 °C and the speed to 40 rpm, and add the following mixing formula: BR 100 parts, zinc oxide 3 parts, stearic acid 2 parts, hollow glass microspheres 10 parts, accelerator NS 1 part, sulfur 1.5 parts, white carbon black 30 parts; (2) Add the formulated materials according to the standard process, wait until the torque is stable, and then perform the debonding at a temperature below 100 °C. Then, unroll the sheet on the open mill and cool it for 24 h to obtain the mixed rubber. (3) The mixed rubber is placed in a flat vulcanizer at 150°C and vulcanized according to the positive vulcanization time tested by the vulcanizer to obtain a vulcanized rubber (i.e., hollow glass microspheres / white carbon black / butadiene rubber composite material).

[0037] Comparative Example 3 Preparation of hollow glass microspheres / carbon black / butadiene rubber composites (1) Set the internal mixer temperature to 100 °C and the speed to 40 rpm, and add the following mixing formula: BR 100 parts, zinc oxide 3 parts, stearic acid 2 parts, hollow glass microspheres 10 parts, accelerator NS 1 part, sulfur 1.5 parts, carbon black 30 parts; (2) Add the formulated materials according to the standard process, wait until the torque is stable, and then perform the debonding at a temperature below 100 °C. Then, unroll the sheet on the open mill and cool it for 24 h to obtain the mixed rubber. (3) The mixed rubber is placed in a flat vulcanizer at 150°C and vulcanized according to the positive vulcanization time tested by the vulcanizer to obtain a vulcanized rubber (i.e., hollow glass microspheres / carbon black / butadiene rubber composite material).

[0038] Performance test 1 Scanning electron microscopy was used to examine the modified hollow glass microspheres prepared in Examples 1-4 with silica coating amounts of 5, 10, 15, and 20%.

[0039] The results obtained are as follows Figure 1 As shown, from Figure 1 It can be seen that after high-temperature calcination, as the concentration of silica adhesion increases, the originally smooth surface of the hollow glass microspheres (a) gradually becomes rough (b~e), and finally a layer of densely coated silica particles is formed on the surface of the hollow glass microspheres, and the particle size of the hollow glass microspheres is about 20~40 μm.

[0040] Performance test 2 The mechanical properties of the hollow glass microspheres / butadiene rubber vulcanizates prepared in Examples 5-8 and Comparative Example 1 were tested.

[0041] The test results are shown in Table 1.

[0042] Table 1 Mechanical properties of hollow glass microspheres / butadiene rubber vulcanizates prepared in Examples 5-8 and Comparative Example 1

[0043] As shown in Table 1, compared with the unmodified rubber compound of Comparative Example 1, the modified hollow glass microspheres / butadiene rubber vulcanizates prepared in Examples 5-8 have reduced density, increased hardness, tensile strength and elongation, and significantly improved wear resistance.

[0044] Performance test 3 The mechanical properties of the hollow glass microspheres / butadiene rubber / silica gel vulcanizates prepared in Examples 9-12 and Comparative Example 2 were tested.

[0045] The test results are shown in Table 2.

[0046] Table 2 Mechanical properties of hollow glass microspheres / silica / butadiene rubber vulcanizates prepared in Examples 9-12 and Comparative Example 2

[0047] As shown in Table 2, compared with Comparative Example 2, the modified hollow glass microspheres / white carbon black / butadiene rubber vulcanizate has improved hardness, tensile stress and wear resistance, reduced density, and slightly decreased tensile strength and elongation.

[0048] Performance test 4 The mechanical properties of the hollow glass microspheres / butadiene rubber / carbon black vulcanizates prepared in Examples 13-16 and Comparative Example 3 were tested.

[0049] The test results are shown in Table 3.

[0050] Table 3 Mechanical properties of hollow glass microspheres / carbon black / butadiene rubber vulcanizates prepared in Examples 13-16 and Comparative Example 3

[0051] From the results in Table 3, it can be seen that compared with Comparative Example 3, the properties of the modified hollow glass microspheres / carbon black / butadiene rubber vulcanizate in terms of hardness, tensile stress, tensile strength, wear resistance and elongation at break are increased, while the density is reduced.

[0052] The principle leading to the improvement of the above mechanical properties is that after the surface of the sintered modified microspheres is coated with white carbon black particles, not only the surface roughness is significantly increased, but also the interface bonding strength between the hollow glass microspheres and the rubber matrix is ​​improved, the proportion of microspheres falling off is reduced, and the wall thickness and strength of the microspheres are increased, and the proportion of breakage is reduced. Figure 1 It can be seen that with the increase of the amount of silica coating on the surface of the hollow glass microspheres, the surrounding defects gradually disappear, the microspheres are gradually "enclosed" by the rubber, and the interface strength with the butadiene rubber matrix increases.

Claims

1. A method for preparing modified hollow glass microspheres coated with silica particles, characterized in that: The method comprises the following steps: (1) Mix hollow glass microspheres and white carbon black in a mass ratio of 1:5-20 and place them in a heating container; (2) Set the muffle furnace temperature to 400-460°C, place the heating container in it, heat it, and then cool it to room temperature to obtain a preliminary sample; (3) Add deionized water to completely immerse the sample, let it stand, and then take the floating components on the upper layer; (4) Drying the upper floating component to obtain modified hollow glass microspheres with a silica particle coating amount of 5-20%.

2. The preparation method according to claim 1, characterized in that In step (2), the heating time is 60 min; In the step (3), the standing time is 30 minutes.

3. A modified hollow glass microsphere coated with silica particles, characterized in that: The modified hollow glass microspheres are prepared by the preparation method according to any one of claims 1 or 2.

4. The modified hollow glass microsphere according to claim 3, characterized in that: The particle size of the modified hollow glass microspheres is 20-40 μm.

5. A modified hollow glass microsphere / rubber composite material, characterized in that: The modified hollow glass microsphere / rubber composite material includes: modified hollow glass microsphere / butadiene rubber composite material, modified hollow glass microsphere / white carbon black / butadiene rubber composite material and modified hollow glass microsphere / carbon black / butadiene rubber composite material; The modified hollow glass microspheres are prepared by the preparation method according to any one of claims 1 or 2.

6. The modified hollow glass microsphere / rubber composite material according to claim 5, characterized in that: The raw materials for preparing the modified hollow glass microsphere / butadiene rubber composite material include, by weight: 100 parts of butadiene rubber, 3 parts of zinc oxide, 2 parts of stearic acid, 10 parts of modified hollow glass microspheres, 1 part of accelerator NS, and 1.5 parts of sulfur.

7. The modified hollow glass microsphere / rubber composite material according to claim 6, characterized in that: The raw materials for preparing the modified hollow glass microspheres / white carbon black / butadiene rubber composite material include, by weight: 100 parts of butadiene rubber, 3 parts of zinc oxide, 2 parts of stearic acid, 10 parts of modified hollow glass microspheres, 1 part of accelerator NS, 1.5 parts of sulfur, and 30 parts of white carbon black.

8. The modified hollow glass microsphere / rubber composite material according to claim 7, characterized in that: The raw materials for preparing the modified hollow glass microspheres / carbon black / butadiene rubber composite material include, by weight: 100 parts of butadiene rubber, 3 parts of zinc oxide, 2 parts of stearic acid, 10 parts of modified hollow glass microspheres, 1 part of accelerator NS, 1.5 parts of sulfur, and 30 parts of carbon black.

9. The modified hollow glass microsphere / rubber composite material according to claim 8, characterized in that: The preparation method of the modified hollow glass microsphere / rubber composite material comprises the following steps: (1) After setting the internal mixer temperature to 80-100 °C and the speed to 40-60 rpm, add the following mixing formula in parts by weight: 100 parts of butadiene rubber, 3 parts of zinc oxide, 2 parts of stearic acid, 10 parts of hollow glass microspheres, 1 part of accelerator NS, 1.5 parts of sulfur, 0-30 parts of white carbon black or carbon black; (2) After mixing evenly, perform debonding at a temperature below 100 °C, then perform tableting and cool for 24 h to obtain a rubber mix; (3) The rubber mixture is placed in a flat plate vulcanizer at 150° C. for vulcanization to obtain the modified hollow glass microsphere / rubber composite material.

10. A method for preparing a modified hollow glass microsphere / rubber composite material, characterized in that: The preparation method of the modified hollow glass microsphere / rubber composite material comprises the following steps: (1) Set the internal mixer temperature to 80-100°C and the speed to 40-60 rpm, and add the following mixing formula: 100 parts of butadiene rubber, 3 parts of zinc oxide, 2 parts of stearic acid, 10 parts of hollow glass microspheres, 1 part of accelerator NS, 1.5 parts of sulfur, 0-30 parts of white carbon black or carbon black; (2) After mixing evenly, perform debonding at a temperature below 100 °C, then perform tableting and cool for 24 h to obtain a rubber mixture; (3) placing the rubber mixture in a flat vulcanizer at 150° C. for vulcanization to obtain the modified hollow glass microsphere / rubber composite material; The modified hollow glass microspheres are prepared by the preparation method according to any one of claims 1 or 2.

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