WO2023184744A1 - Composite microsphere and preparation method therefor - Google Patents

Composite microsphere and preparation method therefor Download PDF

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WO2023184744A1
WO2023184744A1 PCT/CN2022/101176 CN2022101176W WO2023184744A1 WO 2023184744 A1 WO2023184744 A1 WO 2023184744A1 CN 2022101176 W CN2022101176 W CN 2022101176W WO 2023184744 A1 WO2023184744 A1 WO 2023184744A1
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microspheres
composite
expandable microspheres
expandable
preparation
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French (fr)
Chinese (zh)
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刘鑫
成晓军
刘利利
王翔
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快思瑞科技(上海)有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons
    • B01J13/04Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • B01J13/043Drying and spraying
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons
    • B01J13/04Making microcapsules or microballoons by physical processes, e.g. drying, spraying

Definitions

  • the invention relates to a composite microsphere and a method for preparing silicate/organic microsphere composite microspheres.
  • Hollow glass microspheres also known as hollow glass microspheres, glass bubbles, etc., usually refer to hollow microspheres with an average particle size of less than 500 microns and a single cellular structure obtained by firing glass-forming components and foaming agents at high temperatures. Microspheres. Such hollow microspheres have a lower density due to their hollow structure and a certain strength due to their glass structure. For example, the true density of the hollow microspheres disclosed in CN102811965A can be as low as 0.2g/mL and the strength can reach 15,000 psi. CN103415481A discloses the wide application of hollow glass microspheres in industry as regulators, reinforcing agents, fillers, etc.
  • US20130165542A1 and US20150218349A1 disclose glass bubbles and preparation methods.
  • the feed composition when preparing glass bubbles includes SiO 2 , B 2 O 3 and a foaming agent containing sulfur elements.
  • CN103415481A also discloses similar hollow microspheres, and the feed composition during their preparation can include recycled glass particles, boron oxide, and a small amount of sulfur-containing foaming agent.
  • SiO 2 or recycled glass particles are raw materials that can form glass.
  • the temperature of the equipment heating system needs to be above 1300°C to soften the glass-forming components. This high-temperature firing will increase the energy consumption of material preparation.
  • B 2 O 3 or boric acid is a network-forming component of glass.
  • the melting point of boron oxide is 450°C and can be used as a flux.
  • the boron element will remain in the above-mentioned glass bubbles or hollow microspheres, which is limited by the toxicity of boron.
  • the use of glass bubbles or hollow microspheres in hand-made modeling materials such as space sand and ultra-light clay, and CN104520245A mentions that excessive boron in glass microbubbles will hinder the solidification of cement, thus limiting the use of this type of glass microbubbles. Application in cement.
  • Sulfur-containing compounds are effective blowing agents, used to release gas at high temperatures at specific rates and temperatures to interact with the molten glass to create cavities in it, thereby forming hollow microspheres or glass bubbles.
  • the foaming process requires care. Preparation processes that require successful formation of bubbles in the glass component can result in low yields of hollow microspheres.
  • expandable hollow microsphere in the prior art, which has a thermoplastic polymer shell and a low-boiling point core material (such as C1-C12 alkane) inside the shell.
  • This kind of expandable microspheres has two forms: unfoamed and foamed at room temperature.
  • the typical diameter of unfoamed expandable microspheres is 10 to 50 microns, and the true density is 1000 to 1300kg/m 3.
  • Its thermoplastic shell will soften and the volume of the alkanes in the shell will increase, causing the volume of the expandable microspheres to increase to tens to hundreds of times of the unfoamed state, forming foamed expandable microspheres.
  • the above-mentioned foaming process is irreversible. After cooling, the thermoplastic shell of the expandable microspheres hardens, allowing it to maintain the size after foaming.
  • the particle size range increases to 40 to 300 microns, and the true density decreases to 20 to 30kg/m3.
  • This kind of expandable microsphere is airtight at room temperature and has good thermal insulation properties. Since the foamed expandable microsphere has a very small true density, it can be widely used as a lightweight filler in coatings, insulation materials and in the sealing material.
  • the polymer shell of such expandable microspheres is easily damaged by environments such as high temperatures, strong acids, alkalis, or organic solvents, causing the expandable microspheres to lose strength or thermal insulation properties.
  • One of the purposes of the present invention is to solve the problem that the existing glass shell of hollow glass microspheres contains boron element and the expandable microspheres have high molecular polymer shell, resulting in limited use scenarios of both.
  • the present invention provides composite microspheres, which are characterized in that they include expandable microspheres and a silicate layer coating the surface of the expandable microspheres, and the silicate layer does not contain boron and sulfur.
  • the composite microsphere of the present invention has an expandable microsphere inner shell and a silicate outer shell.
  • the silicate outer shell has a protective effect on the expandable microsphere inner shell and can prevent it from being destroyed in high temperature, strong acid and organic solvent environments. Maintain its good thermal conductivity.
  • the expandable microspheres used as the inner shell of the composite microspheres in the present invention are foamed and have a very small true density, which enables the composite microspheres to also be lightweight.
  • the silicate shell does not contain boron, the composite microspheres of the present invention can be used as fillers for handmade toys such as ultra-light clay to ensure the safety of use.
  • expandable microspheres mentioned in the present invention all refer to foamed expandable microspheres.
  • the composite microsphere of the present invention is characterized in that its silicate layer contains silica and alkali metal oxide, wherein the molar ratio of silica to alkali metal oxide is (1.5-4.8):1.
  • the composition of the silicate shell of the composite microspheres can be adjusted by selecting the mixing ratio of silica to alkali metal oxides.
  • alkali metal oxide is selected from at least one of lithium oxide, sodium oxide, and potassium oxide.
  • the above-mentioned expandable microsphere includes a thermoplastic polymer shell and an alkane in the shell.
  • thermoplastic polymer shell can be polymerized from monomers in the presence of an initiator and a cross-linking agent according to the preparation method disclosed in CN112574465A, and the alkanes in the shell can be C4 to C12 alkanes.
  • the diameter of the composite microspheres of the present invention is 40 to 300 microns.
  • the diameter of the composite microspheres mainly depends on the diameter of the foamed expandable microspheres. According to the needs of different usage scenarios, expandable microspheres with different foaming degrees can be used for coating. In addition, changing the thickness of the silicate shell can also appropriately adjust the size of the composite microspheres.
  • the composite microspheres obtained using them as carriers will have a wider size distribution.
  • composite microspheres with a diameter of 40 to 300 microns are screened to meet the needs of actual use.
  • the true density of the composite microspheres of the present invention is 0.02-0.3g/cm 3 .
  • the true density of composite microspheres mainly depends on the degree of foaming of expandable microspheres and the amount of silicate layer. The lower the degree of foaming of expandable microspheres, the thicker the silicate layer coating the surface of composite microspheres. The greater the true density.
  • thermal conductivity of the composite microspheres of the present invention is 0.02-0.05W/(m ⁇ K).
  • the good thermal insulation properties of composite microspheres come from its expandable microsphere inner shell.
  • the thermal conductivity of the selected expandable microspheres is 0.027W/(m ⁇ K), and silicate is formed on the surface. After the coating, due to the good thermal conductivity of inorganic substances, the thermal conductivity of the composite microspheres will increase slightly. The thicker the coating silicate layer, the greater the thermal conductivity of the composite microspheres.
  • Another object of the present invention is to solve the existing problems of high energy consumption in the preparation process of hollow glass microspheres and low yield caused by the preparation method.
  • the present invention provides a method for preparing composite microspheres, which is characterized in that the composite microspheres include expandable microspheres and a silicate layer coating the surface of the expandable microspheres.
  • the above-mentioned preparation method includes the following steps:
  • Coating Add the silicate solution into the paste and stir thoroughly to coat the surface of the expandable microspheres with the silicate solution;
  • Drying Spray dry the expandable microspheres coated with silicate solution to obtain composite microspheres.
  • the composite microspheres of the present invention can be obtained by coating the surface of the expandable microspheres with a silicate solution and spray drying, so that a solidified silicate layer is formed on the surface of the expandable microspheres.
  • High temperature treatment can effectively save energy.
  • a sulfur-containing foaming agent needs to be added to form bubbles in the molten glass component. It is difficult to ensure the integrity of the glass shell.
  • the yield is not high, and the manufacturing method of the present invention uses existing expandable microspheres as carriers, which already have a complete hollow structure.
  • Composite microspheres are obtained after the silicate solution on the surface of the expandable microspheres is dried and solidified. Therefore, The yield rate can be greatly improved.
  • the stirring speed in the above steps is 200-300 r/min, and the total stirring time is 1 hour.
  • the required raw materials are first weighed according to a specific mass ratio, including water, expandable microspheres and silicate solution. Then add the expandable microspheres to the water and stir for 30 minutes at a speed of 300r/min to form a paste. This step slightly moistens the surface of the expandable microspheres, which is conducive to the formation of a uniform silicate solution on the surface of the expandable microspheres in subsequent steps. Covered. Then add the silicate solution to the above paste and stir for 30 minutes at a speed of 200 r/min so that the silicate solution is evenly coated on the surface of the expandable microspheres.
  • a specific mass ratio including water, expandable microspheres and silicate solution.
  • the inlet temperature during spray drying is 150°C
  • the outlet temperature is 80-90°C.
  • conditions such as gas temperature, flow rate, flow shape and pressure as well as material residence time are set according to the moisture content and average particle size of the material.
  • the inlet temperature is set to 150°C
  • the outlet temperature is set to 80-90°C
  • the peristaltic pump pumping speed is set to 20 mL/min.
  • the density of the silicate solution in the above steps is 1.2-1.3g/cm 3 .
  • the silicate solution used is sodium water glass, and its solute can be expressed as Na 2 O ⁇ nSiO 2 .
  • the sodium water The baume degree of glass is 28, and the corresponding density is 1.24g/cm 3 .
  • the mass ratio of the expandable microspheres in the above step to the silicate solution added in the coating step is 1: (1-25).
  • the mass ratio of expandable microspheres and silicate solution is adjusted in order to obtain composite microspheres with different silicate layer thicknesses to meet the needs of different usage scenarios.
  • the above-mentioned silicate layer includes silicon dioxide and alkali metal oxide, wherein the molar ratio of silicon dioxide and alkali metal oxide is (1.5-4.8):1.
  • alkali metal oxide is selected from at least one of lithium oxide, sodium oxide, and potassium oxide.
  • Figure 1 shows an optical microscope photograph of the expandable microspheres in Example 3 of the present invention
  • Figure 2 shows the second optical microscope photo of the expandable microspheres in Example 3 of the present invention
  • Figure 3 shows an optical microscope photograph of the composite microspheres of Example 3 of the present invention
  • Figure 4 shows the second optical microscope photograph of the composite microspheres of Example 3 of the present invention
  • Figure 5 shows an electron micrograph of the composite microspheres of Example 3 of the present invention.
  • the composite microspheres provided in Examples 1-32 of the present invention are all prepared according to the following steps:
  • step S1 the expandable microspheres are provided by Cresir Technology (Shanghai) Co., Ltd.
  • the silicate solution, sodium water glass, and potassium water glass used in the embodiments of the present invention are from Tongxiang Hengli Chemical Co., Ltd.
  • the lithium Water glass comes from Foshan Zhongfa Water Glass Factory.
  • S2 wetting Add the microspheres to water to fully moisten them. Specifically, use a three-blade paddle stirrer to stir, set the stirring speed to 300r/min, and stir for 30 minutes.
  • step S2 the three-blade propeller mixer is an electric mixer HD2004W from Shanghai Sile Instrument Co., Ltd.
  • S3 coating Slowly add the weighed silicate solution to the above solution, adjust the rotation speed to 200r/min, and continue stirring for 30 minutes to evenly coat the surface of the expandable microspheres with the silicate solution.
  • S4 drying The materials obtained in S3 are spray dried in the WPG-1500 laboratory spray dryer through spray drying technology. During spray drying, the inlet temperature is set to 150°C and the outlet temperature is set to 80 ⁇ 90°C. The pump delivery speed was set to 20 mL/min.
  • Table 1 shows the types of raw materials selected in Examples 1-32 of the present invention and their mass proportions in all materials.
  • the mass proportions of raw materials in Table 1 should be understood as: taking Example 1 as an example, the mass parts of all raw materials required to prepare composite microspheres are 60, of which the mass parts of water are 40, and the mass parts of expandable microspheres are The number is 10, and the mass fraction of silicate solution is 10.
  • the D50 value of expandable microspheres in Table 1 is measured after foaming the corresponding brand of microspheres.
  • the grade of the expandable microspheres, the degree of foaming, and the type and modulus used in the silicate solution can be adjusted according to specific needs.
  • the particle size distribution (D50) of the expandable microspheres used in Examples 1-32 was measured in accordance with the GB/T 19077-2016 standard using the laser particle size analyzer LS-609 of Zhuhai Omeike Instrument Co., Ltd.
  • Figures 1-2 show optical microscope photos of the expanded expandable microspheres in Example 3 of the present invention.
  • the diameter of the uncoated expandable microspheres is approximately 20-80 ⁇ m.
  • Figures 3-4 show the embodiment. 3.
  • the diameter of the composite microspheres obtained after coating with silicate layer is approximately 20-150 ⁇ m.
  • Figure 5 shows the electron microscope of the composite microspheres of Example 3. From the photo, it can be seen that the silicate shell of the composite microspheres formed by solution coating and drying is intact.
  • Comparative Example 1 of the present invention uses uncoated expandable microspheres.
  • the expandable microspheres used are expandable microspheres with the brand name 1501 provided by Quesiri Technology (Shanghai) Co., Ltd.
  • Comparative Example 2 uses They are commercially available hollow glass beads with the brand name S15 from 3M Company.
  • True density Use Micromeritics' fully automatic gas displacement true density meter ACCUPYC II 1345 to determine the true density of composite microspheres in accordance with ISO 12154.
  • Thermal conductivity Use Xi'an Xiaxi Electronic Technology Co., Ltd.'s TC3000 series hot-wire method universal thermal conductivity meter TC3100 to measure the thermal conductivity of composite microspheres in accordance with the GB/T 10297-2015 standard.
  • High temperature resistance Put the composite microspheres of Examples 1-32, the expandable microspheres of Comparative Example 1 and the hollow glass microspheres of Comparative Example 2 into the GFX-9245A electric heating drum from Shanghai Modern Environmental Engineering Technology Co., Ltd. In the air drying oven, keep it at 200°C for 30 minutes. Use “ ⁇ ” to indicate that the material morphology is damaged, and “ ⁇ ” to indicate that the material morphology remains intact.
  • Mechanical strength The mechanical strength of the composite microspheres of Examples 1-32, the expandable microspheres of Comparative Example 1, and the hollow glass microspheres of Comparative Example 2 was tested using a multi-purpose sand grinding, dispersing and stirring machine SFJ-400. Specific operating steps: Add 1 volume of the material to be tested and 10 volumes of water into the sand mill, dispersion and mixing machine, stir gently with a glass rod to completely disperse the material to be tested into the water, wait until the liquid level is still, and record Initial material height; then use a dispersing disk for high-speed dispersion, and stir at a speed of 1500r/min for 1 hour; then let it stand for 3 hours until there are no visible bubbles, and observe the changes in the material height.
  • Solvent resistance Soak the composite microspheres of Examples 1-32, the expandable microspheres of Comparative Example 1 and the hollow glass microspheres of Comparative Example 2 in analytically pure DMF solvent for 24 hours, take out the materials and dry them. Observe the appearance of the material under an optical microscope. Use " ⁇ ” to indicate that the morphology of the microspheres to be tested is destroyed, and " ⁇ ” to indicate that the morphology of the microspheres to be tested remains intact.
  • Table 2 shows the performance test results of the composite microspheres of Examples 1-32, the expandable microspheres of Comparative Example 1, and the hollow glass microspheres of Comparative Example 2.
  • the thermoplastic polymer shell of uncoated expandable microspheres is not resistant to acid and high temperature, and will dissolve in organic solvents such as DMF.
  • the silicate shell of the outer layer of the composite microspheres of the present invention can improve the thermoplasticity of the inner layer.
  • the molecular shell provides protection and can improve the shortcomings of organic polymer shells that are not resistant to acids, solvents and high temperatures. Since hollow glass microspheres have a single cell structure and only have one layer of 1-2 micron thick glass shell, their strength is not high and they are easily broken during mechanical stirring. However, the composite microspheres of the present invention have two layers of shells and can effectively The ground remains intact in mechanical agitation.
  • the composite microsphere of the present invention can adjust its thermal conductivity and true density by adjusting the thickness of the silicate layer to meet the needs of different usage scenarios. The thicker the silicate layer, the greater the true density and thermal conductivity. .
  • Example 7 The composite microspheres of Example 7 were selected for a solvent resistance test, and the changes in thermal conductivity of the composite microspheres before and after being soaked in DMF solvent were tested. The data are listed in Table 3.

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Abstract

The present invention provides a composite microsphere, comprising a thermoplastic expandable microsphere and a silicate layer covering the surface of the expandable microsphere, the silicate layer not containing boron and sulfur. The composite microsphere in the present invention is formed by covering the surface of a traditional expandable microsphere with the silicate layer, thus exhibiting the advantages of light weight and good heat preservation performance of said expandable microsphere. Further, since an outer shell of the composite microsphere does not contain boron, the composite microsphere can be used in toys such as space sand and ultra-light clay to improve use safety. The present invention also provides a method for preparing the composite microsphere.

Description

复合微球及其制备方法Composite microspheres and preparation method thereof 技术领域Technical field
本发明涉及一种复合微球以及一种制备硅酸盐/有机微球复合微球的方法。The invention relates to a composite microsphere and a method for preparing silicate/organic microsphere composite microspheres.
背景技术Background technique
空心玻璃微珠,或称中空玻璃微珠、玻璃泡等,通常是指平均粒径在500微米以下的、利用玻璃形成组分和发泡剂在高温下烧制得到的具有单一胞状结构的中空微球体。这种中空微球体因其中空结构而具有较低的密度,因其玻璃结构而具有一定的强度,例如,CN102811965A公开的中空微球体的真密度可低至0.2g/mL,强度可达15000psi。CN103415481A公开了空心玻璃微珠作为调节剂、增强剂、填料等在工业中的广泛应用。Hollow glass microspheres, also known as hollow glass microspheres, glass bubbles, etc., usually refer to hollow microspheres with an average particle size of less than 500 microns and a single cellular structure obtained by firing glass-forming components and foaming agents at high temperatures. Microspheres. Such hollow microspheres have a lower density due to their hollow structure and a certain strength due to their glass structure. For example, the true density of the hollow microspheres disclosed in CN102811965A can be as low as 0.2g/mL and the strength can reach 15,000 psi. CN103415481A discloses the wide application of hollow glass microspheres in industry as regulators, reinforcing agents, fillers, etc.
上述的空心玻璃微珠存在制备方面的一些缺陷。例如,US20130165542A1和US20150218349A1公开了玻璃泡及制备方法,制备玻璃泡时的进料组合物包括SiO 2、B 2O 3和含硫元素的发泡剂。CN103415481A也公开了类似的中空微球体,其制备时的进料组合物可以包括回收玻璃粒子、氧化硼,以及少量含硫的发泡剂。 The above-mentioned hollow glass microspheres have some disadvantages in preparation. For example, US20130165542A1 and US20150218349A1 disclose glass bubbles and preparation methods. The feed composition when preparing glass bubbles includes SiO 2 , B 2 O 3 and a foaming agent containing sulfur elements. CN103415481A also discloses similar hollow microspheres, and the feed composition during their preparation can include recycled glass particles, boron oxide, and a small amount of sulfur-containing foaming agent.
其中,SiO 2或者回收玻璃粒子是能够形成玻璃的原料。在CN103249684A公开的制备中空微球体的方法中,中空微球体烧制时,设备加热系统的温度需要在1300℃以上以使玻璃形成组分软化,这种高温烧制会提高材料制备的能耗。 Among them, SiO 2 or recycled glass particles are raw materials that can form glass. In the method for preparing hollow microspheres disclosed in CN103249684A, when the hollow microspheres are fired, the temperature of the equipment heating system needs to be above 1300°C to soften the glass-forming components. This high-temperature firing will increase the energy consumption of material preparation.
B 2O 3或者硼酸是玻璃的网络形成组分,氧化硼熔点是450℃,可用作助熔剂,但是硼元素会留在上述的玻璃泡或者中空微球体中,因硼的毒性限制了这种玻璃泡或者中空微球体在太空沙、超轻黏土等手工造型材料内的使用,且CN104520245A中提到玻璃微泡中含有过量的硼会妨碍水泥的固化,因此也限制了该种玻璃微泡在水泥中的应用。 B 2 O 3 or boric acid is a network-forming component of glass. The melting point of boron oxide is 450°C and can be used as a flux. However, the boron element will remain in the above-mentioned glass bubbles or hollow microspheres, which is limited by the toxicity of boron. The use of glass bubbles or hollow microspheres in hand-made modeling materials such as space sand and ultra-light clay, and CN104520245A mentions that excessive boron in glass microbubbles will hinder the solidification of cement, thus limiting the use of this type of glass microbubbles. Application in cement.
含硫的化合物是有效的发泡剂,用于在高温下以特定速率和温度释放气体以与熔化的玻璃相互作用在其中产生空腔,从而形成中空微球体或玻璃泡,发泡过程需要小心处理以使玻璃组分中成功形成气泡,这样的制备工艺会导致中空微球体的成品率低。Sulfur-containing compounds are effective blowing agents, used to release gas at high temperatures at specific rates and temperatures to interact with the molten glass to create cavities in it, thereby forming hollow microspheres or glass bubbles. The foaming process requires care. Preparation processes that require successful formation of bubbles in the glass component can result in low yields of hollow microspheres.
现有技术中还存在一种可膨胀的中空微球,具有热塑性聚合物外壳和壳体内的低沸点芯材(如C1~C12烷烃)。这种可膨胀微球在常温下有未发泡和已发泡两种形态,未发泡的可膨胀微球的典型直径为10~50微米,真密度为1000~1300kg/m 3,加热时其热塑性外壳会 软化,壳体内烷烃的体积会增大,使可膨胀微球的体积增加到未发泡状态的数十倍至数百倍,形成已发泡的可膨胀微球。上述发泡过程是不可逆的,冷却后可膨胀微球的热塑性外壳变硬,使其维持发泡后的尺寸,粒径范围增加到40~300微米,真密度减小至20~30kg/m3。这种可膨胀微球在常温下是气密的,具有良好的保温性能,且由于已发泡的可膨胀微球具有非常小的真密度,可以作为轻质填料广泛应用于涂料、保温材料和密封材料中。 There is also an expandable hollow microsphere in the prior art, which has a thermoplastic polymer shell and a low-boiling point core material (such as C1-C12 alkane) inside the shell. This kind of expandable microspheres has two forms: unfoamed and foamed at room temperature. The typical diameter of unfoamed expandable microspheres is 10 to 50 microns, and the true density is 1000 to 1300kg/m 3. When heated, Its thermoplastic shell will soften and the volume of the alkanes in the shell will increase, causing the volume of the expandable microspheres to increase to tens to hundreds of times of the unfoamed state, forming foamed expandable microspheres. The above-mentioned foaming process is irreversible. After cooling, the thermoplastic shell of the expandable microspheres hardens, allowing it to maintain the size after foaming. The particle size range increases to 40 to 300 microns, and the true density decreases to 20 to 30kg/m3. This kind of expandable microsphere is airtight at room temperature and has good thermal insulation properties. Since the foamed expandable microsphere has a very small true density, it can be widely used as a lightweight filler in coatings, insulation materials and in the sealing material.
但是,这种可膨胀微球的高分子聚合物外壳容易被高温、强酸强碱或者有机溶剂等环境破坏,从而导致可膨胀微球丧失强度或者保温性能等。However, the polymer shell of such expandable microspheres is easily damaged by environments such as high temperatures, strong acids, alkalis, or organic solvents, causing the expandable microspheres to lose strength or thermal insulation properties.
发明内容Contents of the invention
本发明的目的之一在于解决现有的空心玻璃微珠的玻璃壳体含有硼元素以及可膨胀微球具有高分子聚合物外壳导致二者使用场景受限的问题。One of the purposes of the present invention is to solve the problem that the existing glass shell of hollow glass microspheres contains boron element and the expandable microspheres have high molecular polymer shell, resulting in limited use scenarios of both.
在第一方面,本发明提供复合微球,其特征在于,包括可膨胀微球和包覆在可膨胀微球表面的硅酸盐层,硅酸盐层不含硼和硫。In a first aspect, the present invention provides composite microspheres, which are characterized in that they include expandable microspheres and a silicate layer coating the surface of the expandable microspheres, and the silicate layer does not contain boron and sulfur.
本发明的复合微球具有可膨胀微球内壳和硅酸盐外壳,硅酸盐外壳对可膨胀微球内壳具有保护作用,可以避免其在高温、强酸以及有机溶剂环境中被破坏,以维持其良好的导热性能。本发明中作为复合微球内壳的可膨胀微球是已发泡的,具有非常小的真密度,能使复合微球也具备质轻的特点。并且,由于硅酸盐外壳中不含硼元素,本发明的复合微球可以作为例如超轻黏土等手工玩具的填料,保证使用的安全性。The composite microsphere of the present invention has an expandable microsphere inner shell and a silicate outer shell. The silicate outer shell has a protective effect on the expandable microsphere inner shell and can prevent it from being destroyed in high temperature, strong acid and organic solvent environments. Maintain its good thermal conductivity. The expandable microspheres used as the inner shell of the composite microspheres in the present invention are foamed and have a very small true density, which enables the composite microspheres to also be lightweight. Moreover, since the silicate shell does not contain boron, the composite microspheres of the present invention can be used as fillers for handmade toys such as ultra-light clay to ensure the safety of use.
如无特殊说明,本发明中提到的可膨胀微球均指已发泡的可膨胀微球。Unless otherwise specified, the expandable microspheres mentioned in the present invention all refer to foamed expandable microspheres.
进一步地,本发明复合微球,其特征在于,其硅酸盐层包含二氧化硅和碱金属氧化物,其中二氧化硅和碱金属氧化物的摩尔比为(1.5~4.8):1。Furthermore, the composite microsphere of the present invention is characterized in that its silicate layer contains silica and alkali metal oxide, wherein the molar ratio of silica to alkali metal oxide is (1.5-4.8):1.
在使用硅酸盐的情况下,可以通过选择二氧化硅与碱金属氧化物的混合比来调整复合微球硅酸盐外壳的组分。In the case of using silicates, the composition of the silicate shell of the composite microspheres can be adjusted by selecting the mixing ratio of silica to alkali metal oxides.
进一步地,上述碱金属氧化物选自锂的氧化物、钠的氧化物、钾的氧化物中的至少一种。Further, the above-mentioned alkali metal oxide is selected from at least one of lithium oxide, sodium oxide, and potassium oxide.
进一步地,上述可膨胀微球包括热塑性聚合物壳体和壳体内的烷烃。Further, the above-mentioned expandable microsphere includes a thermoplastic polymer shell and an alkane in the shell.
示例性地,热塑性聚合物外壳可按照CN112574465A公开的制备方法由单体在引发剂、交联剂的存在下聚合而成,壳体内的烷烃可以是C4~C12烷烃。For example, the thermoplastic polymer shell can be polymerized from monomers in the presence of an initiator and a cross-linking agent according to the preparation method disclosed in CN112574465A, and the alkanes in the shell can be C4 to C12 alkanes.
进一步地,本发明复合微球的直径为40~300微米。Furthermore, the diameter of the composite microspheres of the present invention is 40 to 300 microns.
复合微球的直径主要取决于发泡后的可膨胀微球的直径,根据不同使用场景的需求, 可选用发泡程度不同的可膨胀微球进行包覆。此外,改变硅酸盐外壳的厚度也能对复合微球的尺寸进行适当调节。The diameter of the composite microspheres mainly depends on the diameter of the foamed expandable microspheres. According to the needs of different usage scenarios, expandable microspheres with different foaming degrees can be used for coating. In addition, changing the thickness of the silicate shell can also appropriately adjust the size of the composite microspheres.
根据可膨胀微球的类型和发泡程度不同,以其为载体获得的复合微球会具有较宽的尺寸分布。优选地,在本发明中,筛选直径为40~300微米的复合微球,以满足实际使用的需求。Depending on the type and degree of foaming of expandable microspheres, the composite microspheres obtained using them as carriers will have a wider size distribution. Preferably, in the present invention, composite microspheres with a diameter of 40 to 300 microns are screened to meet the needs of actual use.
进一步地,本发明复合微球的真密度为0.02~0.3g/cm 3Furthermore, the true density of the composite microspheres of the present invention is 0.02-0.3g/cm 3 .
复合微球的真密度主要取决于可膨胀微球的发泡程度和硅酸盐层的量,可膨胀微球的发泡程度越低、表面包覆的硅酸盐层越厚,复合微球的真密度越大。The true density of composite microspheres mainly depends on the degree of foaming of expandable microspheres and the amount of silicate layer. The lower the degree of foaming of expandable microspheres, the thicker the silicate layer coating the surface of composite microspheres. The greater the true density.
进一步地,本发明复合微球的导热系数为0.02~0.05W/(m·K)。Furthermore, the thermal conductivity of the composite microspheres of the present invention is 0.02-0.05W/(m·K).
复合微球良好的保温性来自其可膨胀微球内壳,根据本发明的一个实施例,选用的可膨胀微球的导热系数为0.027W/(m·K),在其表面形成硅酸盐层之后,由于无机物较好的导热性能,会使复合微球的导热系数略有上升,包覆的硅酸盐层越厚,复合微球的导热系数越大。The good thermal insulation properties of composite microspheres come from its expandable microsphere inner shell. According to an embodiment of the present invention, the thermal conductivity of the selected expandable microspheres is 0.027W/(m·K), and silicate is formed on the surface. After the coating, due to the good thermal conductivity of inorganic substances, the thermal conductivity of the composite microspheres will increase slightly. The thicker the coating silicate layer, the greater the thermal conductivity of the composite microspheres.
本发明的另一目的在于解决现有的空心玻璃微珠的制备过程能耗高以及制备方法导致的成品率低的问题。Another object of the present invention is to solve the existing problems of high energy consumption in the preparation process of hollow glass microspheres and low yield caused by the preparation method.
在第二方面,本发明提供复合微球的制备方法,其特征在于,复合微球包括可膨胀微球和包覆在可膨胀微球表面的硅酸盐层,上述制备方法包括如下步骤:In a second aspect, the present invention provides a method for preparing composite microspheres, which is characterized in that the composite microspheres include expandable microspheres and a silicate layer coating the surface of the expandable microspheres. The above-mentioned preparation method includes the following steps:
润湿:将可膨胀微球加入水中搅拌形成膏料;Wetting: Add expandable microspheres to water and stir to form a paste;
包覆:将硅酸盐溶液加入膏料中充分搅拌,使可膨胀微球表面包覆硅酸盐溶液;Coating: Add the silicate solution into the paste and stir thoroughly to coat the surface of the expandable microspheres with the silicate solution;
干燥:喷雾干燥包覆有硅酸盐溶液的可膨胀微球,以获得复合微球。Drying: Spray dry the expandable microspheres coated with silicate solution to obtain composite microspheres.
采用本发明的制备方法,只需在可膨胀微球表面包覆硅酸盐溶液并喷雾干燥,以使可膨胀微球表面形成固化的硅酸盐层即可得到本发明的复合微球,无须高温处理,可以有效节约能源。并且如上所述,在空心玻璃微珠的高温烧制过程中需要添加含硫的发泡剂以在熔融的玻璃组分中形成气泡,难以保证玻璃壳体的完整性,采用这样的烧制方法成品率不高,而本发明的制造方法以现有的可膨胀微球为载体,已经具备完整的空心结构,在可膨胀微球表面的硅酸盐溶液干燥固化后即得到复合微球,因此可以大大提高成品率。Using the preparation method of the present invention, the composite microspheres of the present invention can be obtained by coating the surface of the expandable microspheres with a silicate solution and spray drying, so that a solidified silicate layer is formed on the surface of the expandable microspheres. High temperature treatment can effectively save energy. And as mentioned above, during the high-temperature firing process of hollow glass microspheres, a sulfur-containing foaming agent needs to be added to form bubbles in the molten glass component. It is difficult to ensure the integrity of the glass shell. Using such a firing method The yield is not high, and the manufacturing method of the present invention uses existing expandable microspheres as carriers, which already have a complete hollow structure. Composite microspheres are obtained after the silicate solution on the surface of the expandable microspheres is dried and solidified. Therefore, The yield rate can be greatly improved.
进一步地,上述步骤中搅拌的速度为200~300r/min,搅拌的总时间为1h。Further, the stirring speed in the above steps is 200-300 r/min, and the total stirring time is 1 hour.
具体地,根据本发明的一个实施例,先按照特定的质量比称量所需原料,包括水、可膨胀微球和硅酸盐溶液。然后将可膨胀微球加入到水中以300r/min的速度搅拌30min形成膏料,这一步骤使可膨胀微球表面稍微润湿,有利于后续步骤在可膨胀微球表面形成均匀 硅酸盐溶液包覆。再将硅酸盐溶液加入上述膏料中,以200r/min的速度搅拌30min,使硅酸盐溶液均匀裹覆在可膨胀微球表面。Specifically, according to an embodiment of the present invention, the required raw materials are first weighed according to a specific mass ratio, including water, expandable microspheres and silicate solution. Then add the expandable microspheres to the water and stir for 30 minutes at a speed of 300r/min to form a paste. This step slightly moistens the surface of the expandable microspheres, which is conducive to the formation of a uniform silicate solution on the surface of the expandable microspheres in subsequent steps. Covered. Then add the silicate solution to the above paste and stir for 30 minutes at a speed of 200 r/min so that the silicate solution is evenly coated on the surface of the expandable microspheres.
进一步地,上述步骤中喷雾干燥时的入口温度为150℃,出口温度为80~90℃。Further, in the above steps, the inlet temperature during spray drying is 150°C, and the outlet temperature is 80-90°C.
喷雾干燥过程中气体的温度、流速、流形和压力以及物料停留时间等条件根据物料的含水量、平均粒度等进行设置。根据本发明的一个实施例,喷雾干燥时入口温度设定为150℃,出口温度设定为80~90℃,蠕动泵泵送速度设定为20mL/min。During the spray drying process, conditions such as gas temperature, flow rate, flow shape and pressure as well as material residence time are set according to the moisture content and average particle size of the material. According to an embodiment of the present invention, during spray drying, the inlet temperature is set to 150°C, the outlet temperature is set to 80-90°C, and the peristaltic pump pumping speed is set to 20 mL/min.
进一步地,上述步骤中硅酸盐溶液的密度为1.2~1.3g/cm 3Further, the density of the silicate solution in the above steps is 1.2-1.3g/cm 3 .
根据本发明的一个实施例,使用的硅酸盐溶液是钠水玻璃,其溶质可表示为Na 2O·nSiO 2,其中钠水玻璃的模数为3.8,也即n=3.8,该钠水玻璃的波美度为28,对应的密度为1.24g/cm 3According to one embodiment of the present invention, the silicate solution used is sodium water glass, and its solute can be expressed as Na 2 O·nSiO 2 . The modulus of the sodium water glass is 3.8, that is, n=3.8. The sodium water The baume degree of glass is 28, and the corresponding density is 1.24g/cm 3 .
进一步地,上述步骤中可膨胀微球与包覆步骤中加入的硅酸盐溶液的质量比为1:(1~25)。Further, the mass ratio of the expandable microspheres in the above step to the silicate solution added in the coating step is 1: (1-25).
在本发明的实施例中,调节可膨胀微球与硅酸盐溶液的质量比是为了获得具有不同硅酸盐层厚度的复合微球,以满足不同使用场景的需求。In embodiments of the present invention, the mass ratio of expandable microspheres and silicate solution is adjusted in order to obtain composite microspheres with different silicate layer thicknesses to meet the needs of different usage scenarios.
进一步地,上述硅酸盐层包含二氧化硅和碱金属氧化物,其中,二氧化硅和碱金属氧化物的摩尔比为(1.5~4.8):1。Further, the above-mentioned silicate layer includes silicon dioxide and alkali metal oxide, wherein the molar ratio of silicon dioxide and alkali metal oxide is (1.5-4.8):1.
进一步地,上述碱金属氧化物选自锂的氧化物、钠的氧化物、钾的氧化物中的至少一种。Further, the above-mentioned alkali metal oxide is selected from at least one of lithium oxide, sodium oxide, and potassium oxide.
附图说明Description of drawings
图1示出本发明实施例3的可膨胀微球的光学显微镜照片一;Figure 1 shows an optical microscope photograph of the expandable microspheres in Example 3 of the present invention;
图2示出本发明实施例3的可膨胀微球的光学显微镜照片二;Figure 2 shows the second optical microscope photo of the expandable microspheres in Example 3 of the present invention;
图3示出本发明实施例3的复合微球的光学显微镜照片一;Figure 3 shows an optical microscope photograph of the composite microspheres of Example 3 of the present invention;
图4示出本发明实施例3的复合微球的光学显微镜照片二;Figure 4 shows the second optical microscope photograph of the composite microspheres of Example 3 of the present invention;
图5示出本发明实施例3的复合微球的电镜照片。Figure 5 shows an electron micrograph of the composite microspheres of Example 3 of the present invention.
具体实施方式Detailed ways
以下由特定的具体实施例说明本发明的实施方式,本领域技术人员可由本说明书所揭示的内容轻易地了解本发明的其他优点及功效。虽然本发明的描述将结合较佳实施例一起介绍,但这并不代表此发明的特征仅限于该实施方式。恰恰相反,结合实施方式作发明介 绍的目的是为了覆盖基于本发明的权利要求而有可能延伸出的其它选择或改造。为了提供对本发明的深度了解,以下描述中将包含许多具体的细节。本发明也可以不使用这些细节实施。此外,为了避免混乱或模糊本发明的重点,有些具体细节将在描述中被省略。需要说明的是,在不冲突的情况下,本发明中的实施例及实施例中的特征可以相互组合。The implementation of the present invention is described below with specific examples. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. Although the present invention will be described in conjunction with preferred embodiments, this does not mean that the features of the invention are limited to this embodiment. On the contrary, the purpose of introducing the invention in conjunction with the embodiments is to cover other options or modifications that may be extended based on the claims of the invention. The following description contains numerous specific details in order to provide a thorough understanding of the invention. The invention may be practiced without these details. Furthermore, some specific details will be omitted from the description in order to avoid confusing or obscuring the focus of the present invention. It should be noted that, as long as there is no conflict, the embodiments and features in the embodiments of the present invention can be combined with each other.
下面将结合具体的实施例对本发明的复合微球及其制备方法做进一步地解释和说明,然而该解释和说明并不对本发明的技术方案构成不当限定。The composite microspheres and their preparation methods of the present invention will be further explained and described below with reference to specific examples. However, this explanation and description do not unduly limit the technical solution of the present invention.
本发明的实施例1-32中提供的复合微球均按照如下步骤制备得到:The composite microspheres provided in Examples 1-32 of the present invention are all prepared according to the following steps:
S1配料:按表1所示的质量百分比称取原料,包括水、可膨胀微球和硅酸盐溶液。S1 Ingredients: Weigh the raw materials according to the mass percentage shown in Table 1, including water, expandable microspheres and silicate solution.
在步骤S1中,可膨胀微球由快思瑞科技(上海)有限公司提供,本发明实施例中使用的硅酸盐溶液、钠水玻璃、钾水玻璃来自桐乡市恒立化工有限公司,锂水玻璃来自佛山中发水玻璃厂。In step S1, the expandable microspheres are provided by Cresir Technology (Shanghai) Co., Ltd., the silicate solution, sodium water glass, and potassium water glass used in the embodiments of the present invention are from Tongxiang Hengli Chemical Co., Ltd., and the lithium Water glass comes from Foshan Zhongfa Water Glass Factory.
S2润湿:将微球加入到水中充分润湿,具体地,采用三叶桨搅拌器进行搅拌,设定搅拌速度为300r/min,搅拌30min。S2 wetting: Add the microspheres to water to fully moisten them. Specifically, use a three-blade paddle stirrer to stir, set the stirring speed to 300r/min, and stir for 30 minutes.
在步骤S2中,三叶桨搅拌器是来自上海司乐仪器有限公司的电动搅拌机HD2004W。In step S2, the three-blade propeller mixer is an electric mixer HD2004W from Shanghai Sile Instrument Co., Ltd.
S3包覆:将称量好的硅酸盐溶液缓慢加入到上述溶液中,将转速调整至200r/min,继续搅拌30min,使可膨胀微球表面均匀包覆硅酸盐溶液。S3 coating: Slowly add the weighed silicate solution to the above solution, adjust the rotation speed to 200r/min, and continue stirring for 30 minutes to evenly coat the surface of the expandable microspheres with the silicate solution.
S4干燥:将S3中获得的物料通过喷雾干燥技术,在WPG-1500实验室喷雾干燥机中进行喷雾干燥,喷雾干燥时入口温度设定为150℃,出口温度设定为80~90℃,蠕动泵泵送速度设定为20mL/min。S4 drying: The materials obtained in S3 are spray dried in the WPG-1500 laboratory spray dryer through spray drying technology. During spray drying, the inlet temperature is set to 150°C and the outlet temperature is set to 80~90°C. The pump delivery speed was set to 20 mL/min.
表1示出本发明实施例1-32中选用的原料的类型及在全部物料中的质量比例。Table 1 shows the types of raw materials selected in Examples 1-32 of the present invention and their mass proportions in all materials.
表1.Table 1.
Figure PCTCN2022101176-appb-000001
Figure PCTCN2022101176-appb-000001
Figure PCTCN2022101176-appb-000002
Figure PCTCN2022101176-appb-000002
表1中原料的质量比例应当理解为:以实施例1为例,制备复合微球所需的全部原料的质量份数为60,其中水的质量份数为40,可膨胀微球的质量份数为10,硅酸盐溶液的质量份数为10。表1中可膨胀微球的D50值是相应牌号的微球经发泡后测得的。The mass proportions of raw materials in Table 1 should be understood as: taking Example 1 as an example, the mass parts of all raw materials required to prepare composite microspheres are 60, of which the mass parts of water are 40, and the mass parts of expandable microspheres are The number is 10, and the mass fraction of silicate solution is 10. The D50 value of expandable microspheres in Table 1 is measured after foaming the corresponding brand of microspheres.
本发明中,可膨胀微球的牌号、发泡程度以及用于硅酸盐溶液的类型和模数都可以根据具体的需求进行调整。In the present invention, the grade of the expandable microspheres, the degree of foaming, and the type and modulus used in the silicate solution can be adjusted according to specific needs.
实施例1-32中使用的可膨胀微球的粒径分布(D50)使用珠海欧美克仪器有限公司的激光粒度分析仪LS-609按照GB/T 19077-2016标准进行测定。The particle size distribution (D50) of the expandable microspheres used in Examples 1-32 was measured in accordance with the GB/T 19077-2016 standard using the laser particle size analyzer LS-609 of Zhuhai Omeike Instrument Co., Ltd.
图1-2示出本发明实施例3的发泡后的可膨胀微球的光学显微镜照片,未经包覆的可膨胀微球的直径大约在20~80μm,图3-4示出实施例3可膨胀微球包覆硅酸盐层后的光学显微镜照片,包覆硅酸盐层后获得的复合微球的直径大约在20~150μm,图5示出实施例3的复合微球的电镜照片,可以看出通过溶液包覆并干燥形成的复合微球的硅酸盐外壳是完好无损的。Figures 1-2 show optical microscope photos of the expanded expandable microspheres in Example 3 of the present invention. The diameter of the uncoated expandable microspheres is approximately 20-80 μm. Figures 3-4 show the embodiment. 3. Optical microscope photo of expandable microspheres after coating with silicate layer. The diameter of the composite microspheres obtained after coating with silicate layer is approximately 20-150 μm. Figure 5 shows the electron microscope of the composite microspheres of Example 3. From the photo, it can be seen that the silicate shell of the composite microspheres formed by solution coating and drying is intact.
在获得复合微球后,按下述方法对其性能进行测试,结果记载在表2中。After obtaining the composite microspheres, their performance was tested according to the following method, and the results are recorded in Table 2.
本发明的对比例1使用的是未包覆的可膨胀微球,采用的可膨胀微球是快思瑞科技(上海)有限公司提供的牌号为1501的可膨胀微球,对比例2使用的是市售的来自3M公司牌号为S15的空心玻璃微珠。Comparative Example 1 of the present invention uses uncoated expandable microspheres. The expandable microspheres used are expandable microspheres with the brand name 1501 provided by Quesiri Technology (Shanghai) Co., Ltd. Comparative Example 2 uses They are commercially available hollow glass beads with the brand name S15 from 3M Company.
真密度:使用Micromeritics的全自动气体置换法真密度仪ACCUPYC II 1345按照ISO 12154测定复合微球的真密度。True density: Use Micromeritics' fully automatic gas displacement true density meter ACCUPYC II 1345 to determine the true density of composite microspheres in accordance with ISO 12154.
导热系数:使用西安夏溪电子科技有限公司的TC3000系列热线法通用型导热系数仪TC3100按照GB/T 10297-2015标准测定复合微球的导热系数。Thermal conductivity: Use Xi'an Xiaxi Electronic Technology Co., Ltd.'s TC3000 series hot-wire method universal thermal conductivity meter TC3100 to measure the thermal conductivity of composite microspheres in accordance with the GB/T 10297-2015 standard.
耐高温性能:将实施例1-32的复合微球、对比例1的可膨胀微球以及对比例2的空心玻璃微珠放入来自上海现代环境工程技术有限公司的GFX-9245A型电加热鼓风干燥箱中,在200℃下保持30min,用“×”表示材料形貌被破坏,用“√”表示材料形貌保持完好。High temperature resistance: Put the composite microspheres of Examples 1-32, the expandable microspheres of Comparative Example 1 and the hollow glass microspheres of Comparative Example 2 into the GFX-9245A electric heating drum from Shanghai Modern Environmental Engineering Technology Co., Ltd. In the air drying oven, keep it at 200°C for 30 minutes. Use “×” to indicate that the material morphology is damaged, and “√” to indicate that the material morphology remains intact.
耐酸性:将实施例1-32的复合微球、对比例1的可膨胀微球以及对比例2的空心玻璃微珠在pH=2的盐酸溶液中浸泡24h,其中,盐酸溶液和待测样品的体积比约为10:1。用“×”表示材料形貌被破坏,用“√”表示材料形貌保持完好。Acid resistance: Soak the composite microspheres of Examples 1-32, the expandable microspheres of Comparative Example 1, and the hollow glass microspheres of Comparative Example 2 in a hydrochloric acid solution of pH=2 for 24 hours, where the hydrochloric acid solution and the sample to be tested The volume ratio is approximately 10:1. Use "×" to indicate that the material morphology is destroyed, and use "√" to indicate that the material morphology remains intact.
机械强度:采用砂磨分散搅拌多用机SFJ-400对实施例1-32的复合微球、对比例1的可膨胀微球以及对比例2的空心玻璃微珠进行机械强度检测。具体的操作步骤:将1体积的待测物料和到10体积的水加入到砂磨分散搅拌多用机中,用玻璃棒轻轻搅拌,使待测物料完全分散到水中,待液面静止,记录初始的物料高度;再用分散盘进行高速分散,在1500r/min的转速下搅拌1h;然后静置3h直至无可见气泡,观察物料高度的变化,如物料高度降低,则表明待测微球出现破碎,如物料高度保持不变,则表明待测微球仍保持完整,用“×”表示搅拌后物料高度下降、复合微球球壳有破损,用“√”表示搅拌后物料高度不变、待测微球球壳完整。Mechanical strength: The mechanical strength of the composite microspheres of Examples 1-32, the expandable microspheres of Comparative Example 1, and the hollow glass microspheres of Comparative Example 2 was tested using a multi-purpose sand grinding, dispersing and stirring machine SFJ-400. Specific operating steps: Add 1 volume of the material to be tested and 10 volumes of water into the sand mill, dispersion and mixing machine, stir gently with a glass rod to completely disperse the material to be tested into the water, wait until the liquid level is still, and record Initial material height; then use a dispersing disk for high-speed dispersion, and stir at a speed of 1500r/min for 1 hour; then let it stand for 3 hours until there are no visible bubbles, and observe the changes in the material height. If the material height decreases, it indicates that the microspheres to be measured appear. Broken. If the height of the material remains unchanged, it means that the microspheres to be tested are still intact. Use “×” to indicate that the height of the material has dropped after stirring and the shell of the composite microsphere is damaged. Use “√” to indicate that the height of the material remains unchanged after stirring. The shell of the microsphere to be tested is complete.
耐溶剂性:将实施例1-32的复合微球、对比例1的可膨胀微球以及对比例2的空心玻璃微珠放入分析纯的DMF溶剂中浸泡24h,捞出物料并干燥后在光学显微镜下观察物料的外观,用“×”表示待测微球形貌被破坏,用“√”表示待测微球形貌保持完好。Solvent resistance: Soak the composite microspheres of Examples 1-32, the expandable microspheres of Comparative Example 1 and the hollow glass microspheres of Comparative Example 2 in analytically pure DMF solvent for 24 hours, take out the materials and dry them. Observe the appearance of the material under an optical microscope. Use "×" to indicate that the morphology of the microspheres to be tested is destroyed, and "√" to indicate that the morphology of the microspheres to be tested remains intact.
表2示出实施例1-32的复合微球、对比例1的可膨胀微球以及对比例2的空心玻璃微珠的性能测试结果。Table 2 shows the performance test results of the composite microspheres of Examples 1-32, the expandable microspheres of Comparative Example 1, and the hollow glass microspheres of Comparative Example 2.
表2.Table 2.
Figure PCTCN2022101176-appb-000003
Figure PCTCN2022101176-appb-000003
Figure PCTCN2022101176-appb-000004
Figure PCTCN2022101176-appb-000004
未包覆的可膨胀微球的热塑性聚合物外壳不耐酸、不耐高温,且会在如DMF等有机溶剂中溶解,本发明的复合微球外层的硅酸盐壳体能对内层热塑性高分子壳体提供保护,可以改善有机高分子壳体不耐酸、不耐溶剂和高温的缺点。空心玻璃微珠由于具有单一的胞状结构,只有一层1~2微米厚的玻璃壳体,强度不高,容易在机械搅拌中破碎,而本发明的复合微球有两层壳体,能够有效地在机械搅拌中保持完整的结构。此外,本发明的复合微球能通过调整硅酸盐层的厚度来调整其导热系数以及真密度,以满足不同使用场景的需求,其中,硅酸盐层越厚,真密度和导热系数越大。The thermoplastic polymer shell of uncoated expandable microspheres is not resistant to acid and high temperature, and will dissolve in organic solvents such as DMF. The silicate shell of the outer layer of the composite microspheres of the present invention can improve the thermoplasticity of the inner layer. The molecular shell provides protection and can improve the shortcomings of organic polymer shells that are not resistant to acids, solvents and high temperatures. Since hollow glass microspheres have a single cell structure and only have one layer of 1-2 micron thick glass shell, their strength is not high and they are easily broken during mechanical stirring. However, the composite microspheres of the present invention have two layers of shells and can effectively The ground remains intact in mechanical agitation. In addition, the composite microsphere of the present invention can adjust its thermal conductivity and true density by adjusting the thickness of the silicate layer to meet the needs of different usage scenarios. The thicker the silicate layer, the greater the true density and thermal conductivity. .
选取实施例7的复合微球进行耐溶剂性试验,并测试该复合微球经DMF溶剂浸泡前后导热系数的变化,数据列于表3中。The composite microspheres of Example 7 were selected for a solvent resistance test, and the changes in thermal conductivity of the composite microspheres before and after being soaked in DMF solvent were tested. The data are listed in Table 3.
表3table 3
Figure PCTCN2022101176-appb-000005
Figure PCTCN2022101176-appb-000005
由表3的结果可以看出,DMF浸泡前后复合微球的导热系数并无明显变化,可以证实复合微球的耐溶剂性,复合微球的硅酸盐外壳能对可膨胀微球内壳提供有效保护。It can be seen from the results in Table 3 that there is no significant change in the thermal conductivity of the composite microspheres before and after soaking in DMF, which can confirm the solvent resistance of the composite microspheres. The silicate shell of the composite microspheres can provide a protective layer for the inner shell of the expandable microspheres. Effective protection.
虽然通过参照本发明的某些优选实施方式,已经对本发明进行了图示和描述,但本领域的普通技术人员应该明白,以上内容是结合具体的实施方式对本发明所作的进一步详细说明,不能认定本发明的具体实施只局限于这些说明。本领域技术人员可以在形式上和细节上对其作各种改变,包括做出若干简单推演或替换,而不偏离本发明的精神和范围。Although the present invention has been illustrated and described with reference to certain preferred embodiments of the present invention, those of ordinary skill in the art should understand that the above content is a further detailed description of the present invention in conjunction with specific embodiments and cannot be deemed to be Specific implementations of the invention are limited only to these descriptions. Those skilled in the art can make various changes in form and details, including making several simple deductions or substitutions, without departing from the spirit and scope of the invention.

Claims (13)

  1. 复合微球,包括可膨胀微球和包覆在所述可膨胀微球表面的硅酸盐层,所述硅酸盐层不含硼和硫。Composite microspheres include expandable microspheres and a silicate layer coating the surface of the expandable microspheres, and the silicate layer does not contain boron and sulfur.
  2. 根据权利要求1所述的复合微球,所述硅酸盐层包含二氧化硅和碱金属氧化物,其中,二氧化硅和碱金属氧化物的摩尔比为(1.5~4.8):1。The composite microsphere according to claim 1, wherein the silicate layer contains silica and alkali metal oxide, wherein the molar ratio of silica to alkali metal oxide is (1.5-4.8):1.
  3. 根据权利要求2所述的复合微球,所述碱金属氧化物选自锂的氧化物、钠的氧化物、钾的氧化物中的至少一种。The composite microsphere according to claim 2, wherein the alkali metal oxide is selected from at least one selected from the group consisting of lithium oxide, sodium oxide, and potassium oxide.
  4. 根据权利要求1-3中任一项所述的复合微球,所述可膨胀微球包括热塑性聚合物壳体和壳体内的烷烃。The composite microsphere according to any one of claims 1 to 3, said expandable microsphere comprising a thermoplastic polymer shell and an alkane within the shell.
  5. 根据权利要求1-3中任一项所述的复合微球,其直径为40~300微米。The composite microsphere according to any one of claims 1 to 3 has a diameter of 40 to 300 microns.
  6. 根据权利要求1-3中任一项所述的复合微球,其真密度为0.02~0.3g/cm 3The composite microsphere according to any one of claims 1 to 3 has a true density of 0.02 to 0.3 g/cm 3 .
  7. 根据权利要求1-3中任一项所述的复合微球,其导热系数为0.02~0.05W/(m·K)。The composite microsphere according to any one of claims 1 to 3 has a thermal conductivity of 0.02 to 0.05 W/(m·K).
  8. 复合微球的制备方法,其中所述复合微球包括可膨胀微球和包覆在所述可膨胀微球表面的硅酸盐层,所述制备方法包括如下步骤:A method for preparing composite microspheres, wherein the composite microspheres comprise expandable microspheres and a silicate layer coating the surface of the expandable microspheres. The preparation method includes the following steps:
    润湿:将所述可膨胀微球加入水中搅拌形成膏料;Wetting: add the expandable microspheres to water and stir to form a paste;
    包覆:将硅酸盐溶液加入所述膏料中充分搅拌,使所述可膨胀微球表面包覆硅酸盐溶液;Coating: add the silicate solution into the paste and stir thoroughly so that the surface of the expandable microspheres is coated with the silicate solution;
    干燥:喷雾干燥包覆有硅酸盐溶液的可膨胀微球,以获得所述复合微球。Drying: Spray dry the expandable microspheres coated with the silicate solution to obtain the composite microspheres.
  9. 根据权利要求8所述的制备方法,其中搅拌的速度为200~300r/min,在所述润湿步骤中,控制所述搅拌的时间为20~40分钟;在所述包覆步骤中,控制所述搅拌的时间为20~40分钟。The preparation method according to claim 8, wherein the stirring speed is 200-300r/min, in the wetting step, the stirring time is controlled to be 20-40 minutes; in the coating step, the stirring time is controlled to be 20-40 minutes. The stirring time is 20 to 40 minutes.
  10. 根据权利要求8或9所述的制备方法,其中喷雾干燥时的入口温度为150℃,出口温度为80~90℃。The preparation method according to claim 8 or 9, wherein the inlet temperature during spray drying is 150°C and the outlet temperature is 80-90°C.
  11. 根据权利要求8或9所述的制备方法,其中所述可膨胀微球与所述包覆步骤中加入的硅酸盐溶液的质量比为1:(1~25)。The preparation method according to claim 8 or 9, wherein the mass ratio of the expandable microspheres to the silicate solution added in the coating step is 1: (1-25).
  12. 根据权利要求8-11中任一项所述的制备方法,其中所述硅酸盐层包含二氧化硅和碱金属氧化物,其中,二氧化硅和碱金属氧化物的摩尔比为(1.5~4.8):1。The preparation method according to any one of claims 8-11, wherein the silicate layer contains silicon dioxide and alkali metal oxides, wherein the molar ratio of silicon dioxide and alkali metal oxides is (1.5~ 4.8): 1.
  13. 根据权利要求12所述的制备方法,其中所述碱金属氧化物选自锂的氧化物、钠的氧化物、钾的氧化物中的至少一种。The preparation method according to claim 12, wherein the alkali metal oxide is selected from at least one of lithium oxide, sodium oxide, and potassium oxide.
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