Organic silicon modified glass bead and application thereof in silicone adhesive

Abstract

The invention provides an organic silicon modified glass bead and an application thereof in a silicone adhesive. The organic silicon modified glass beads comprise hollow glass beads and organic silicon grafted on the surfaces of the hollow glass beads, and preparation raw materials of the organic silicon comprise a silicone oil modifier with the solid content of 25%-34% and a platinum catalyst, the silicone oil modifier comprises 100 parts by mass of vinyl silicone oil, 26-30 parts by mass of hydrogen-containing silicone oil, 3-5 parts by mass of vinyl trimethoxy silane and a first organic solvent. The organic silicon modified glass beads have large surface roughness, and can be combined with a silicone adhesive matrix through chemical bonds and stably dispersed in the silicone adhesive when being applied to the silicone adhesive as a matting agent, so that the surface roughness of the cured silicone adhesive is increased, the matting effect is good, and the long-acting matting effect is realized; and after being stored for a long time, the matte silicone adhesive still has a relatively good matting effect and good storage stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the application field of hollow glass microspheres, and in particular to a silicone-modified glass microsphere and application of the same in a silicone sealant. BACKGROUND

[0002] As a commonly used organic silicon sealing material, silicone sealant is widely used in many fields such as building, electronics, automobiles, etc. due to its excellent weather resistance, high and low temperature resistance, electrical insulation and good adhesion. However, in some application scenarios such as high-end decoration and electronic device shell sealing, there are specific requirements for the gloss of the surface of the silicone sealant. Excessive gloss will affect the appearance and performance of the product, so the silicone sealant needs to be matt treated. The common matt methods for silicone sealant mainly include adding matt powder and controlling curing conditions. However, due to the poor compatibility of the existing matt powder with the silicone sealant matrix, the structure of the matt powder is unstable and it is easy to agglomerate, which will cause the gloss to rise over time, so the silicone sealant containing matt powder has the following two problems: The first problem: after long-term storage, the matt effect cannot be maintained, and the storage stability of the silicone sealant is poor. In order to solve this problem, the existing technology usually prepares the matt sealant on site, and does not store it in advance. The second problem: the matt film formed by the newly prepared silicone sealant has good matt effect on the surface, but the matt effect inside is poor, and the matt effect may disappear if the surface is scratched. Therefore, the patent application CN115785890A discloses a matt sealant and a preparation method and application thereof. The preparation raw materials of the matt sealant, by mass fraction, include 40-60 parts of α, ω-dihydroxy polydimethylsiloxane, 40-60 parts of calcium carbonate, 2-10 parts of a plasticizer and a matt powder. The matt powder includes 5-15 parts of a first matt powder and / or 15-30 parts of a second matt powder. The first matt powder includes silicon dioxide, and the particle size of the silicon dioxide is 3-30 μm. The second matt powder includes at least one of silicon powder, mica powder and talc powder, and the particle size of the second matt powder is 10-50 μm. By selecting specific types and specific particle sizes of the matt powder, the absorption and diffuse reflection of light by the sealant can be maximized, most of the light is diffusely reflected and absorbed, and the matt effect is achieved. The matt sealant prepared has good matt effect from the inside to the outside.

[0003] Although the above-mentioned patent application solves the second problem of the silicone sealant containing matt powder in the prior art, it does not solve the first problem. Therefore, when using the matt silicone sealant containing matt powder, it is best to prepare and use it on site in order to ensure the matt effect of the product. However, preparing and using the matt silicone sealant on site affects the construction efficiency. SUMMARY

[0004] Therefore, the present application mainly adopts a silicone oil modifier to modify the hollow glass microspheres, grafts the silicone on the surface of the hollow glass microspheres to form the silicone modified glass microspheres; the silicone modified glass microspheres have a large surface roughness, as a matting agent, are applied to the silicone adhesive, can be combined with the silicone adhesive matrix through a chemical bond, are stably dispersed in the silicone adhesive, so that not only the surface roughness of the silicone adhesive after curing is increased, the matting effect is good, and the long-acting matte effect is realized; and the matte silicone adhesive still has a good matting effect and good storage stability after long-term storage.

[0005] Therefore, the present application provides a silicone modified glass microsphere and application thereof in a silicone adhesive.

[0006] Specifically, the technical solution of the present application is as follows: A silicone modified glass microsphere comprises hollow glass microspheres and silicone grafted on the surface of the hollow glass microspheres, and the preparation raw material of the silicone comprises a silicone oil modifier with a solid content of 25% to 34% and a platinum catalyst, wherein the silicone oil modifier comprises 100 parts by mass of vinyl silicone oil, 26 to 30 parts by mass of hydrogen-containing silicone oil, 3 to 5 parts by mass of vinyl trimethoxysilane, and a first organic solvent.

[0007] In order to provide a reaction site and construct a polymer skeleton, the content of the vinyl group in the vinyl silicone oil is 2.0 mol% to 2.5 mol%, and the viscosity is 100 to 200 cSt.

[0008] In order to provide a reaction site and construct a network structure, the hydrogen content in the hydrogen-containing silicone oil is 0.35 mol% to 0.37 mol%, and the viscosity is 10 to 20 cSt.

[0009] In order to reduce the surface gloss and enhance the matte effect of the silicone adhesive in the subsequent use process, the D 90 The particle size is preferably 100 to 120 μm, and the true density is 0.13 to 0.27 g / cm 2 .

[0010] A preparation method of the above-mentioned silicone modified glass microspheres comprises: uniformly mixing the silicone oil modifier, the platinum catalyst and the hollow glass microspheres, allowing the vinyl silicone oil, the hydrogen-containing silicone oil and the vinyl trimethoxysilane to generate a silicone molecular chain containing siloxane groups and silicon hydrogen groups through a silicon hydrogen addition reaction under the action of the catalyst, allowing the siloxane groups in the silicone molecular chain to react with the hydroxyl groups on the surface of the hollow glass microspheres, so that the silicone is grafted on the surface of the hollow glass microspheres to form the silicone modified glass microspheres.

[0011] In order to improve the grafting efficiency of the organic silicon on the surface of the hollow glass microsphere, the preparation method comprises the following steps: rotating the hollow glass microsphere, spraying the silicone modifier and the platinum catalyst on the surface of the rotating hollow glass microsphere, uniformly mixing the silicone modifier and the platinum catalyst, and reacting at 80-110 DEG C for 3-5 hours.

[0012] In order to ensure the modification effect, the mass ratio of the hollow glass microsphere to the silicone modifier is 25-34:1.

[0013] The application of the organic silicon modified glass microsphere in the matt silicone glue, wherein the silicone glue is a condensation type silicone glue.

[0014] The raw materials of the matt silicone glue comprise 100 parts by mass of 2w107 glue, 10 parts by mass of 201 phenolic resin, 15-20 parts by mass of methyl trimethoxysilane, 3-5 parts by mass of the organic silicon modified glass microsphere, 0.4-0.8 parts by mass of an organic metal catalyst, 80-100 parts by mass of calcium carbonate and 2.5-3 parts by mass of carbon black.

[0015] The preparation method of the matt silicone glue comprises the following steps: uniformly mixing all the raw materials, degassing the raw materials under vacuum, and then storing the raw materials in a tube.

[0016] The main reason why the silicone glue containing the organic silicon modified glass microsphere can realize long-term matt effect is that the organic silicon modified glass microsphere is modified on the surface of the hollow glass microsphere, so that the surface of the glass microsphere contains a large number of silicon-oxygen-silicon structures, and contains silicon-hydrogen bonds and silicon-hydroxyl groups which can react with the silicone glue matrix, so that the silicone glue matrix can be grafted to the surface of the glass microsphere during the glue preparation process.

[0017] Further, the silicon-hydrogen bond and the silicon-hydroxyl on the surface of the organic silicon modified glass microbead react with the silicone glue under the action of an organic metal catalyst to form stable chemical covalent bonds instead of simple physical mixing; the chemical bonds can avoid the agglomeration or sedimentation of the glass microbead in the glue, and the structure is very stable and not easy to be damaged, so that the uniform dispersion effect is maintained for a long time, so that the matte silicone glue still has stable extinction effect after long-term storage, and has good storage stability; meanwhile, the roughness of the surface of the cured silicone glue is increased to realize long-acting matte effect.

[0018] Further, the organic silicon modified glass microbead introduces a silicon-oxygen-silicon structure group which is compatible with the silicone glue matrix and a silicon-hydrogen bond and a silicon-hydroxyl which can react with the silicone glue matrix, so that the silicone glue matrix is grafted to the surface of the glass microbead during glue preparation, and then the hollow glass microbead is perfectly combined with the silicone glue matrix, so as to improve the mechanical properties of the silicone glue. Therefore, the above technical solution provided by the present application modifies the surface of the hollow glass microbead by a specific organic silicon resin, so that the hollow glass microbead can be better combined with the silicone glue matrix while being stably dispersed in the silicone glue for a long time, so that the silicone glue has long-term storage stability, good extinction stability, and good mechanical properties. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 The microscope photo of the organic silicon modified glass microbead provided for the embodiment 1 of the present application; Figure 2 The photo of the silicone glue provided for the embodiment 1 of the present application after being placed for 1 h (left) and 15 d (right); Figure 3 The photo of the silicone glue provided for the comparative example 1 of the present application after being placed for 1 h (left) and 15 d (right); Figure 4 The photo of the silicone glue provided for the comparative example 2 of the present application after being placed for 1 h (left) and 15 d (right); Figure 5 The photo of the silicone glue provided for the comparative example 3 of the present application after being placed for 1 h (left) and 15 d (right); Figure 6 The photo of the silicone glue provided for the embodiment 2 of the present application after being placed for 1 h (left) and 15 d (right); Figure 7 The photo of the silicone glue provided for the embodiment 3 of the present application after being placed for 1 h (left) and 15 d (right). DETAILED DESCRIPTION

[0020] In order to make the purpose, technical scheme and advantages of the present application clearer, the technical scheme of the present application will be described clearly and completely in combination with the embodiments of the present application.

[0021] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0022] In this invention, unless otherwise specified and / or stated, all numerical values ​​involving component amounts are "by weight". Unless otherwise specified, the terminology used in this invention are common terms in the relevant field. Unless otherwise specified, the preparation processes, testing methods, etc., used in the various embodiments are conventional methods well known to those skilled in the art, and the raw materials and equipment used can be obtained from publicly available commercial sources.

[0023] Existing silicone sealants typically have a glossy, smooth surface after curing, reflecting light. Matte finishes break this smoothness, creating a rougher surface for a matte effect. Hollow glass microspheres, being micron-sized particles, are directly distributed within the silicone sealant. During curing, they protrude from the surface, forming an uneven structure that visually creates a matte effect. However, ordinary hollow glass microspheres have poor compatibility with the silicone sealant matrix, resulting in poor adsorption of molecular chains during colloid movement. Consequently, after long-term storage and reuse, the hollow glass microspheres easily detach from the cured silicone sealant, making it difficult to achieve a stable matte finish over a long period.

[0024] To achieve the above objectives, the technical solution of the present invention will be further described in detail below through specific embodiments.

[0025] An organosilicon-modified glass microsphere comprises hollow glass microspheres and organosilicon grafted onto the surface of the hollow glass microspheres. The raw materials for preparing the organosilicon include a silicone oil modifier with a solid content of 25% to 34% and a platinum catalyst. The silicone oil modifier comprises 100 parts by weight of vinyl silicone oil, 26 to 30 parts by weight of hydrogen-containing silicone oil, 3 to 5 parts by weight of vinyltrimethoxysilane, and a first organic solvent.

[0026] If the content of vinyl in the vinyl silicone oil is too large, the reaction is incomplete, too much unreacted vinyl remains in the system, which affects the stability of the adhesive; if the content is too small, there are not enough active groups to react with the hydrogen-containing silicone oil by silicon hydrogen addition reaction, which cannot form enough chemical bonds on the surface of the microbeads, resulting in weakened interfacial bonding force between the microbeads and the silicone adhesive matrix, affecting the mechanical properties of the silicone adhesive; therefore, the content of vinyl in the vinyl silicone oil is preferably 2.0 mol% to 2.5 mol%, such as 2.5 mol%, 2.4 mol%, 2.3 mol%, 2.2 mol%, 2.1 mol%, etc.

[0027] If the viscosity content of the vinyl silicone oil is too large, it will be difficult to disperse, and a vinyl compound with too large viscosity will lead to uneven dispersion on the surface of the hollow glass microbeads, making it difficult to form a uniform modified layer, thereby affecting the consistency of the modification effect; if it is too small, it may not be enough to crosslink the silicon hydrogen addition reaction, thereby affecting the mechanical properties of the silicone adhesive; therefore, the viscosity of the vinyl silicone oil is preferably 100 to 200 cSt, such as 100 cSt, 120 cSt, 140 cSt, 150 cSt, 160 cSt, 180 cSt, 200 cSt, etc.

[0028] If the amount of the hydrogen-containing silicone oil is too large, on the one hand, it can react with the vinyl silicone oil under the catalysis of Pt, and on the other hand, it can react with the silicone adhesive matrix to produce more silicon hydroxyl groups; if it is too small, the interfacial bonding force is insufficient and the modification effect is not obvious; therefore, the amount of the hydrogen-containing silicone oil is limited to 26 to 30 parts by mass, such as 26 parts by mass, 27 parts by mass, 28 parts by mass, 29 parts by mass, 30 parts by mass, etc. The hydrogen content in the hydrogen-containing silicone oil is preferably 0.35 mol% to 0.37 mol%. If the viscosity of the hydrogen-containing silicone oil is too large, the Si-H of the hydrogen-containing silicone oil and the vinyl group are difficult to fully contact and collide, greatly reducing the reaction rate, and the viscosity is too large, making it difficult to achieve uniform mixing by stirring, which can lead to incomplete local reaction and poor modification effect; if it is too small, the flowability is excellent, the mixing is fast, and the molecular movement is more free, the active group Si-H can react with the vinyl group faster, thereby accelerating the reaction rate; therefore, the viscosity of the hydrogen-containing silicone oil is preferably 10-20 cSt, such as 10 cSt, 12 cSt, 14 cSt, 15 cSt, 16 cSt, 18 cSt, 20 cSt, etc.

[0029] The main purpose of adding the first organic solvent in the silicone oil modifier is to adjust the solid content; if the solid content is too high, the concentration is too high, which leads to poor modification effect; if the solid content is too low, it will be diluted too much, resulting in low modification efficiency; therefore, the solid content is limited to 25% to 34%. The first organic solvent includes but is not limited to toluene, xylene, isopropyl alcohol, etc.

[0030] The platinum catalyst mainly aims to catalyze the silicon hydrogen addition reaction of the vinyl silicone oil, hydrogen-containing silicone oil and vinyl trimethoxysilane, and successfully graft on the hollow glass microbeads.

[0031] If the particle size of the hollow glass microbeads is small, it is difficult to achieve the matte effect of the silicone adhesive; if the particle size is large, the bonding strength between the silicone adhesive and the adherend is affected; therefore, the D 90 The particle size is preferably 100-120 μm, and the true density is 0.13-0.27 g / cm 2 For example, the microbeads HL15, HL20 and HL25.

[0032] A preparation method of the above-mentioned organic silicon modified glass microbeads, comprising: uniformly mixing the silicone oil modifier, platinum catalyst and hollow glass microbeads, allowing the vinyl silicone oil, hydrogen-containing silicone oil and vinyl trimethoxysilane to undergo silicon hydrogen addition reaction under the action of the catalyst to generate an organic silicon molecular chain containing siloxane groups and silicon hydrogen groups, allowing the siloxane groups in the organic silicon molecular chain to react with the hydroxyl groups on the surface of the hollow glass microbeads, so that the hollow glass microbeads are grafted with organic silicon on the surface to form the organic silicon modified glass microbeads.

[0033] In a specific embodiment, the hollow glass microbeads are modified by the impregnation method, for example, the hollow glass microbeads are first uniformly dispersed in the silicone oil modifier, and then the platinum catalyst is slowly added, so that the vinyl silicone oil, hydrogen-containing silicone oil and vinyl trimethoxysilane in the system react, and the organic silicon is grafted to the surface of the hollow glass microbeads.

[0034] In another specific embodiment, the organic silicon is grafted to the surface of the hollow glass microbeads by the spraying method, specifically comprising the following steps: Component preparation: the vinyl silicone oil, hydrogen-containing silicone oil, vinyl trimethoxysilane and the first organic solution are uniformly stirred and mixed to obtain a modifier component with a solid content of 25%-34%; the metal catalyst is added to the second organic solvent, and stirred and uniformly mixed to form a platinum catalyst, and the mass ratio of the metal catalyst to the second organic solvent is 0.2:20-30; Microbead modification: the hollow glass microbeads are rotated, the silicone oil modifier and the platinum catalyst are simultaneously sprayed to the surface of the hollow glass microbeads rotating at a speed of 6-12 r / min to uniformly mix, and the spraying is completed within 60 min, and the organic silicon modified glass microbeads are formed by reacting at a constant temperature of 80-110℃ for 3-5 h.

[0035] The main purpose of the second organic solvent is to uniformly disperse the metal catalyst, which includes but is not limited to anhydrous ethanol, isopropyl alcohol, ethylene glycol and tetrahydrofuran.

[0036] If the amount of the hollow glass microspheres is too large, the modification is not complete, and the surface of the microspheres is not completely coated; if the amount of the hollow glass microspheres is too small, the amount of the silicone oil modifier is relatively large, which not only causes the post-processing to be troublesome due to the excess of the silicone oil modifier, and requires more complex cleaning and drying steps to remove the excess modifier, but also affects the close combination between the microspheres and the matrix due to the steric hindrance effect, and the cost of the modifier is much higher than that of the hollow glass microspheres; therefore, the mass ratio of the hollow glass microspheres to the silicone oil modifier is 25-34:1. In this way, the silicone oil modifier generates sufficient active sites for the modified glass microspheres, which is sufficient to improve the dispersibility of the glass microspheres in the silicone adhesive, and reduces the raw material cost under the premise of ensuring the modification effect.

[0037] The above silicone-modified glass microspheres have a large amount of siloxane structure on the surface of the hollow glass microspheres, and contain silane hydrogen bonds and silicon hydroxyl groups that can react with the silicone adhesive matrix, so that the silicone adhesive matrix can be grafted to the surface of the glass microspheres during the preparation of the adhesive. In this way, on the one hand, since the surface of the silicone adhesive after curing is usually glossy, and the particle size of the modified glass microspheres is micron-level particles, the above silicone-modified glass microspheres can be used as a matting agent in the silicone adhesive to reduce the gloss of the silicone adhesive; on the other hand, the glass microspheres can avoid agglomeration or sedimentation in the adhesive, and the structure is very stable and not easy to be damaged, which ensures that the uniform dispersion effect is maintained for a long time, and after long-term storage, the glass microspheres still have good matting effect, so that they have long-term stable matting effect; in addition, the silicone adhesive matrix is grafted to the surface of the glass microspheres during the preparation of the silicone adhesive, so that the glass microspheres are closely combined with the silicone adhesive matrix, thereby improving the mechanical properties of the silicone adhesive.

[0038] Therefore, the application provides application of the above-mentioned organic silicon modified glass microbead in silicone glue extinction, wherein the silicone glue is a condensation type silicone glue. The silicone glue is preferably a condensation type single-component silicone glue. Since the curing reaction of the condensation type silicone glue is based on the reaction of silanol groups with moisture in the air to release small molecules, thereby realizing cross-linking and curing, after the addition of the organic silicon modified glass microbead, the condensation reaction can proceed normally. Moreover, the surface of the organic silicon modified glass microbead contains a large amount of siloxane structure, and simultaneously contains silicon hydrogen bonds and silicon hydroxyl groups which can react with the base glue of the condensation type silicone glue, so that the base glue of such silicone glue can be grafted to the surface of the glass microbead during glue preparation; therefore, the organic silicon modified glass microbead can be used as an extinction agent and applied to silicone glue, can be stably dispersed in the silicone glue for a long time, still has long-term stable extinction effect after long-term storage, and simultaneously maintains the mechanical properties of the silicone glue. A extinction silicone glue, raw materials of which include: 100 parts by mass of 2w107 glue, 10 parts by mass of 201 phenolic resin, 15-20 parts by mass of methyltrimethoxysilane, 3-5 parts by mass of the above-mentioned organic silicon modified glass microbead, 0.4-0.8 parts by mass of an organic metal catalyst, 80-100 parts by mass of calcium carbonate and 2.5-3 parts by mass of carbon black.

[0039] The 201 phenolic resin is mainly used in cooperation with the 2w107 glue to achieve the purposes of adjusting the viscosity of the silicone glue and providing a basic skeleton. The main function of the organic metal catalyst is to accelerate the curing process of the silicone glue into an elastic solid after contacting with air moisture, so as to ensure that cross-linking and film forming can be completed within a practical time, and the organic metal catalyst can be dibutyltin dilaurate, dibutyltin dioctoate or tetraisopropyl titanate.

[0040] The main function of the methyltrimethoxysilane is a cross-linking agent which determines the basic mechanical properties of the glue and enables the glue to be cured and shaped, and the amount of the methyltrimethoxysilane has an important influence on the curing of the silicone glue, so the amount of the methyltrimethoxysilane is limited to 15-20 parts by mass, such as 15 parts by mass, 16 parts by mass, 17 parts by mass, 18 parts by mass, 19 parts by mass or 20 parts by mass.

[0041] If the amount of the above-mentioned organic silicon modified glass microbead is too large, the mechanical properties of the silicone glue will be significantly deteriorated; if the amount is too small, the effect will not be significant; therefore, the amount of the organic silicon modified glass microbead is limited to 3-5 parts by mass.

[0042] The main function of the calcium carbonate is a reinforcing filler, and in order to improve the hardness and strength of the silicone glue, if the amount of the calcium carbonate is too large, the silicone glue will be too viscous to be extruded, and if the amount is too small, the reinforcing effect will be poor; therefore, the amount of the calcium carbonate is limited to 80-100 parts by mass, such as 80 parts by mass, 85 parts by mass, 90 parts by mass, 95 parts by mass or 100 parts by mass. The particle size of the calcium carbonate is 50-200 nm.

[0043] The main role of carbon black is to provide stable and persistent black appearance, and its amount has an important influence on the color of the silicone adhesive. Therefore, the amount of calcium carbonate is limited to 2.5-3 parts by mass, such as 2.5 parts by mass, 2.6 parts by mass, 2.7 parts by mass, 2.8 parts by mass, 2.9 parts by mass, 3 parts by mass, etc. The particle size of the carbon black is 20-50 nm.

[0044] A preparation method of the above-mentioned matte silicone adhesive comprises uniformly mixing all raw materials, degassing under vacuum for 20-40 min, then filling the tube and sealing, and extruding for curing at room temperature for 24-48 h when used, to obtain the matte silicone adhesive.

[0045] The hollow glass microspheres in the following examples and comparative examples are all from Zhengzhou Shenglaite Hollow Microsphere New Material Co., Ltd.

[0046] Example 1 This example provides a silicone-modified glass microsphere S1 and a preparation method thereof, and the specific scheme is as follows: I. Component configuration Silicone oil modifier component: uniformly mix 100 parts of vinyl silicone oil RH-vi100, 30 parts of hydrogen-containing silicone oil RH-536, 5 parts of vinyl trimethoxysilane, and 270 parts of toluene by mass parts, to obtain the modifier component; Platinum catalyst: uniformly mix 0.2 parts of platinum and 20 parts of anhydrous ethanol by mass parts, to obtain the platinum catalyst; II. Preparation of modified hollow glass microspheres: Spray the silicone oil modifier component and the catalyst component onto the hollow glass microspheres HL20 (particle size 110 μm, true density 0.18-0.22 g / cm 2 ) at a mass ratio of 3:1 at the same time, to obtain the silicone-modified glass microspheres S1, as shown in Figure 1 In this step, the modification process of the glass microspheres is rotary mixing, the rotation speed is 10 r / min, the mixing reaction temperature is 105 ℃, the spraying time is within 60 min, the reaction time is 5 h, and the mass ratio of the hollow glass microspheres HL20 to the silicone oil modifier component is 25:1.

[0047] Example 2 The embodiment provides a kind of organic silicon modified glass bead S2 and its preparation method, which is basically same with the organic silicon modified glass bead and its preparation method provided in embodiment 1, the main difference is that in this embodiment, the amount of hydrogen-containing silicone oil RH-536 in silicone oil modifier component is 26 parts by mass, vinyl trimethoxysilane 3 parts by mass, toluene 350 parts, the amount of anhydrous ethanol in platinum catalyst is 30 parts by mass;Modifier component and platinum catalyst are according to mass ratio 4:1;The preparation step of modified hollow glass bead adopts the hollow glass bead model HL25, the mass ratio of the hollow glass bead HL25 and silicone oil modifier component is 30:1, and the reaction time is 3h;The same.

[0048] Embodiment 3 The embodiment provides a kind of organic silicon modified glass bead S3 and its preparation method, which is basically same with the organic silicon modified glass bead and its preparation method provided in embodiment 1, the main difference is that in this embodiment, the amount of hydrogen-containing silicone oil RH-536 in silicone oil modifier component is 28 parts by mass, vinyl trimethoxysilane 4 parts by mass, toluene 330 parts, the amount of anhydrous ethanol in platinum catalyst is 25 parts by mass;Modifier component and platinum catalyst are according to mass ratio 3.5:1;The preparation step of modified hollow glass bead adopts the hollow glass bead model HL15, the mass ratio of the hollow glass bead HL15 and silicone oil modifier component is 34:1, and the reaction time is 4h;The same.

[0049] Application Example 1 The application embodiment provides an application of the organic silicon modified glass bead provided in embodiment 1 in silicone glue extinction. Specifically, the application embodiment provides a matte silicone glue YG1 and a preparation method thereof, and the specific scheme is as follows: 100 parts of 2w107 glue, 10 parts of 201 resin, 15 parts of methyl trimethoxysilane, 5 parts of the above-mentioned organic silicon modified glass bead, 0.4 parts of dibutyltin dilaurate, 80 parts of calcium carbonate and 2.8 parts of carbon black are uniformly mixed in a reaction kettle to form a mixture; the mixture is degassed under vacuum for 30 min, and the kettle is taken out to obtain the matte silicone glue.

[0050] Application Example 2 The application embodiment provides a matte silicone glue YG2 and a preparation method thereof, which are basically same with the matte silicone glue YG1 and the preparation method thereof, and the main difference is that 4 parts of the organic silicon modified glass bead S1 is added in the matte silicone glue YG2, and the others are the same.

[0051] Application Example 3 The application embodiment provides a matte silicone adhesive YG3 and a preparation method thereof, which are basically the same as the matte silicone adhesive YG1 and the preparation method thereof, and the main difference is that 3 parts of silicone modified glass microbeads S2 are added, and the other conditions are the same.

[0052] Application Example 4 The application embodiment provides a matte silicone adhesive YG4 and a preparation method thereof, which are basically the same as the matte silicone adhesive YG1 and the preparation method thereof, and the main difference is that 20 parts of methyltrimethoxysilane, 4 parts of silicone modified glass microbeads S3, 0.8 parts of tetraisopropyl titanate phthalate and 100 parts of calcium carbonate are added to the matte silicone adhesive YG2, and the other conditions are the same.

[0053] Application Comparative Examples 1-3 Application Comparative Examples 1-3 each provide a silicone adhesive DYG and a preparation method thereof, which are basically the same as the matte silicone adhesive YG1 and the preparation method thereof, and the main difference is as follows: 5 parts of unmodified HL20 microbeads are added to the matte silicone adhesive DYG1, and the other conditions are the same; No hollow glass microbeads are added to the silicone adhesive DYG2, and the other raw materials and steps remain unchanged, and the silicone adhesive DYG2 is prepared; No hollow glass microbeads are added to the matte silicone adhesive DYG3, but 5 parts of silica matting powder are added, and the other conditions are the same; wherein the particle size of the silica matting powder is 7-9 μm, and the true density is 2.2 g / cm 2 .

[0054] Performance detection: the silicone adhesives provided in Application Examples 1-4 and Comparative Examples 1-3 are detected as follows, and the results are shown in Table 1.

[0055] Sample preparation and curing: GB / T 13477.1-2003 Sample tensile strength and breaking strength test standard: GB / T 13477.8 "Building sealant test method" Density test standard: GB / T 13354-1992 Adhesive density determination method-weighing cup method Matting test: the corresponding silicone adhesive is cured for 0-15 days (d), and the curing conditions are temperature: 23℃±2℃, humidity: 50±5%; the cured silicone adhesive is extruded onto A4 paper, folded and flattened, the A4 paper is opened, and the surface state of the adhesive is observed after curing for 24 h at room temperature, and the gloss of the silicone adhesive is recorded by taking a photo, as shown in Figures 2~7 .

[0056] Table 1 Performance detection results of silicone adhesives Sample Tensile strength / MPa Elongation at break / % Density / g.cm -3 ]] Quenching effect after 1 h extrusion curing Quenching effect after 15 d extrusion curing YG1(-S1) 0.70 119.73 1.35 Good Good YG2(-S1) 0.71 124.52 1.39 Good Good YG3(-S2) 0.72 135.10 1.45 Good Good YG4(-S3) 0.71 128.50 1.36 Good Good DYG1 0.68 91.96 1.34 Poor Poor DYG2 0.74 162.33 1.55 Poor Poor DYG3 0.73 153.45 1.56 Good Poor

[0057] Combined Figures 2~7and the test results shown in Table 1 can know that: the silicone glue YG1~4 provided by the application application example still has good extinction effect after long-term storage. The glossiness of the silicone glue YG1~3 prepared by the application example is significantly lower than that of the comparative example DYG1~3, which shows that the modified hollow glass microsphere provided by the application example has excellent extinction effect; at the same time, the density of the silicone glue YG1~3 is lower than that of the comparative example silicone glue DYG2~3 under the premise of maintaining good mechanical properties, which reflects the advantage of the modified hollow glass microsphere in improving the comprehensive performance of the silicone glue; and the extinction effect of example 1 and example 2 is obviously better than that of comparative example 3 after 15 days of storage, which shows that the organic silicon modified glass microsphere has better stability in the silicone glue, and the extinction performance after long-term storage is also more stable.

[0058] The matte silicone glue provided by the application application example has long-term extinction effect and good mechanical strength, and the main reasons are as follows: The organic silicon modified glass microsphere S1~3 provided by the application example is modified on the surface of the hollow glass microsphere, so that the surface contains a large number of silicon-oxygen-silicon structures which are compatible with 107 glue, and also contains silicon-hydrogen bonds and silicon-hydroxyl groups which can react with 107 glue, so that 107 glue can be grafted to the surface of the glass microsphere during glue preparation; because the surface of the silicone glue is usually glossy after curing, and the particle size of the modified glass microsphere is micron-level particles, the above-mentioned organic silicon modified glass microsphere can be used as an extinction agent and applied to the silicone glue to effectively increase the surface roughness of the silicone glue, so that the silicone glue presents a matte effect visually.

[0059] In addition, the organic silicon modified glass microsphere S1~3 provided by the application example can undergo addition reaction with 107 glue to form stable chemical covalent bonds, rather than simple physical mixing; such chemical bonds can avoid the agglomeration or sedimentation of glass microspheres in the glue, and the structure is very stable and not easy to be damaged, ensuring that the uniform dispersion effect is maintained for a long time, so that it still has long-term stable extinction effect after long-term storage, so that the silicone glue can be stored for a long time and has good stability.

[0060] Further, the organic silicon modified glass microsphere S1~3 provided by the application example not only has a silicon-oxygen-silicon structure on its surface which is compatible with 107 glue, but also has silicon-hydrogen bonds and silicon-hydroxyl groups which can react with 107 glue and graft 107 glue to the surface of the glass microsphere, so that the glass microsphere is fully combined with 107 glue, thereby improving the mechanical properties of the silicone glue.

[0061] It should be pointed out finally that the above examples are only used to illustrate the technical solutions of the present application but not to limit it; although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the specific embodiments of the present application can be modified or some technical features can be replaced by equivalent ones without departing from the spirit of the technical solutions of the present application, and all of them should be covered in the technical solution range claimed by the present application.

Claims

1. A silicone-modified glass microsphere, characterized by, The organic silicon is grafted on the surface of the hollow glass microsphere, and the raw material of the organic silicon comprises a silicone oil modifier with a solid content of 25-34% and a platinum catalyst, wherein the silicone oil modifier comprises 100 parts by mass of a vinyl silicone oil, 26-30 parts by mass of a hydrogen-containing silicone oil, 3-5 parts by mass of a vinyl trimethoxysilane and a first organic solvent.

2. The silicone-modified glass microbead of claim 1, wherein, The vinyl silicone oil has a vinyl content of 2.0-2.5 mol% and a viscosity of 100-200 cSt.

3. The silicone-modified glass microbead according to claim 1 or 2, characterized in that, The hydrogen-containing silicone oil has a hydrogen content of 0.35-0.37 mol% and a viscosity of 10-20 cSt.

4. The silicone-modified glass microbead of claim 1, wherein, The hollow glass microbeads have a D 90 The particle diameter is preferably 100 to 120 μm, and the true density is 0.13 to 0.27 g / cm 2 .

5. A method of making the silicone-modified glass microbeads of any one of claims 1-4, comprising: The silicone oil modifier, the platinum catalyst and the hollow glass microsphere are uniformly mixed, the vinyl silicone oil, the hydrogen-containing silicone oil and the vinyl trimethoxysilane are subjected to a silicon-hydrogen addition reaction under the action of the platinum catalyst to generate an organic silicon molecular chain containing siloxane groups and silicon-hydrogen groups, and the siloxane groups in the organic silicon molecular chain react with the hydroxyl groups on the surface of the hollow glass microsphere so that the hollow glass microsphere is grafted with organic silicon to form silicone-modified glass microspheres.

6. The production method according to claim 5, characterized by The method comprises the following steps: The hollow glass microspheres are rotated, the silicone oil modifier and the platinum catalyst are simultaneously sprayed onto the surface of the rotating hollow glass microspheres to be uniformly mixed, and the reaction is carried out at 80-110°C for 3-5 h; wherein the platinum catalyst is composed of 0.2 parts by mass of platinum and 20-30 parts by mass of a second organic solvent.

7. The production method according to claim 6, characterized by, The mass ratio of the hollow glass microspheres to the silicone oil modifier is 25-34:

1.

8. Use of the silicone-modified glass microbeads according to any one of claims 1 to 4 for matting silicone gums, wherein, The silicone adhesive is a condensation type silicone adhesive.

9. A matte silicone gum characterized in that, The raw material comprises: 2w107 glue 100 parts by mass, 201 phenolic resin 10 parts by mass, methyl trimethoxysilane 15-20 parts by mass, the silicone-modified glass microspheres according to any one of claims 1-4 3-5 parts by mass, organic metal catalyst 0.4-0.8 parts by mass, calcium carbonate 80-100 parts by mass and carbon black 2.5-3 parts by mass.

10. A method of preparing the matte silicone gum of claim 9, comprising: All the raw materials are uniformly mixed and degassed under vacuum, and then are packed and stored, and when used, are extruded and cured at room temperature for 24-48 h to obtain a matte silicone adhesive.

Images