CN105969196A - Hydroxyapatite ultralong nanowire composite inflaming retarding and damping paint - Google Patents
Hydroxyapatite ultralong nanowire composite inflaming retarding and damping paint Download PDFInfo
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- 238000013016 damping Methods 0.000 title claims abstract description 123
- 239000002070 nanowire Substances 0.000 title claims abstract description 117
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 115
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 115
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000003973 paint Substances 0.000 title claims description 15
- 230000000979 retarding effect Effects 0.000 title 1
- 239000002994 raw material Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 107
- 239000011248 coating agent Substances 0.000 abstract description 91
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 58
- 239000003063 flame retardant Substances 0.000 abstract description 58
- 230000009467 reduction Effects 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 6
- 230000009477 glass transition Effects 0.000 description 15
- 239000002002 slurry Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
本发明涉及一种羟基磷灰石超长纳米线复合阻燃阻尼涂料，所述复合阻燃阻尼涂料以羟基磷灰石超长纳米线和阻尼涂料为原料复合得到，所述羟基磷灰石超长纳米线的长度为10～1000微米，单个羟基磷灰石超长纳米线的直径为5～100纳米，羟基磷灰石超长纳米线占所述复合阻燃阻尼涂料的重量百分比为1～50 wt.%。本发明的羟基磷灰石超长纳米线复合阻燃阻尼涂料具有阻燃、力学增强、减振和降噪等效果，在飞机、轨道列车、汽车和船舶等多个领域具有良好的应用前景。
The invention relates to a hydroxyapatite ultra-long nanowire composite flame-retardant damping coating. The length of the long nanowire is 10-1000 micrometers, the diameter of a single hydroxyapatite ultra-long nanowire is 5-100 nanometers, and the weight percentage of the hydroxyapatite ultra-long nanowire in the composite flame-retardant damping coating is 1-100 micrometers. 50 wt.%. The hydroxyapatite ultra-long nanowire composite flame-retardant damping coating of the present invention has the effects of flame retardancy, mechanical enhancement, vibration reduction and noise reduction, and has good application prospects in various fields such as aircraft, rail trains, automobiles and ships.
Description
技术领域technical field
本发明属于涂料领域，涉及一种阻燃阻尼涂料，具体涉及一种羟基磷灰石超长纳米线复合阻燃阻尼涂料。The invention belongs to the field of coatings, and relates to a flame-retardant damping coating, in particular to a hydroxyapatite ultra-long nanowire composite flame-retardant damping coating.
背景技术Background technique
随着科学技术的快速发展和人们生活水平的提高，高速、自动化的机械设备和振动工具在日常生活中日益增多，由此产生的振动和噪音问题也日益严重。振动和噪声激振共振响应直接影响电子仪器和仪表的正常运作，严重时造成生产事故；振动引发的噪音危害人体健康。采用阻尼材料或阻尼结构进行减振降噪是解决上述问题的一个重要手段。With the rapid development of science and technology and the improvement of people's living standards, high-speed, automated mechanical equipment and vibration tools are increasingly used in daily life, and the resulting vibration and noise problems are also becoming more and more serious. Vibration and noise excitation and resonance response directly affect the normal operation of electronic instruments and meters, and in severe cases cause production accidents; the noise caused by vibration is harmful to human health. Using damping materials or damping structures to reduce vibration and noise is an important means to solve the above problems.
由高分子聚合物材料混合制备而成的阻尼涂料具有优异的减振、降噪等特点。阻尼涂料涂覆在金属结构表面可以减振降噪，其工作原理是阻尼涂料吸收振动机械能，将其转化成热能而耗散。随着飞机和轨道列车等机械运行速度的提高，振动愈加严重，阻尼涂料吸收转化的热能大幅增加。许多高分子聚合物为易燃物，不具有阻燃性能，存在火灾隐患。因此，研发新型阻燃阻尼涂料具有重要的意义和良好的应用前景。The damping coating prepared by mixing high molecular polymer materials has excellent vibration and noise reduction characteristics. Damping coatings coated on the surface of metal structures can reduce vibration and noise. Its working principle is that damping coatings absorb vibrational mechanical energy, convert it into heat energy and dissipate it. As the speed of machinery such as airplanes and rail trains increases, the vibration becomes more serious, and the heat energy absorbed and transformed by the damping coating increases significantly. Many polymers are flammable, do not have flame retardancy, and have fire hazards. Therefore, it is of great significance and good application prospect to develop new flame-retardant and damping coatings.
发明内容Contents of the invention
面对现有技术中存在的上述问题，本发明的目的在于提供一种新型的阻燃阻尼涂料，具体是一种具有阻燃性能的羟基磷灰石超长纳米线复合阻燃阻尼涂料。Facing the above-mentioned problems in the prior art, the object of the present invention is to provide a novel flame-retardant damping coating, specifically a flame-retardant hydroxyapatite ultra-long nanowire composite flame-retardant damping coating.
在此，本发明提供一种羟基磷灰石超长纳米线复合阻燃阻尼涂料，所述复合阻燃阻尼涂料具有阻燃性能，所述复合阻燃阻尼涂料以羟基磷灰石超长纳米线和阻尼涂料为原料复合得到，所述羟基磷灰石超长纳米线的长度为10～1000微米，单个羟基磷灰石超长纳米线的直径为5～100纳米，羟基磷灰石超长纳米线的重量占所述复合阻燃阻尼涂料百分含量为1～50wt.％，优选5～25wt.％。Here, the present invention provides a hydroxyapatite ultra-long nanowire composite flame-retardant damping coating, the composite flame-retardant damping coating has flame-retardant properties, and the composite flame-retardant damping coating uses hydroxyapatite ultra-long nanowire Composite with damping paint as raw material, the length of the hydroxyapatite superlong nanowire is 10-1000 microns, the diameter of a single hydroxyapatite superlong nanowire is 5-100 nanometers, and the hydroxyapatite superlong nanowire The weight of the wire accounts for 1-50wt.%, preferably 5-25wt.%, of the composite flame-retardant damping coating.
本发明采用具有良好的生物相容性、环境友好、阻燃性能优良的阻燃原料羟基磷灰石超长纳米线与阻尼涂料作为原料，通过复合得到具有阻燃性能的羟基磷灰石超长纳米线复合阻燃阻尼涂料。本发明中，羟基磷灰石超长纳米线耐高温并且不燃烧，与阻尼涂料复合后可以提高复合阻燃阻尼涂料的阻燃性能。并且，羟基磷灰石超长纳米线具有独特的一维超长纳米结构，可以改善阻尼涂料的力学性能。羟基磷灰石是一种重要的生物材料，具有良好的生物相容性，环境友好，呈现优良的白色，可以改善阻尼涂料的白度。此外，羟基磷灰石超长纳米线与阻尼涂料的复合可以拓宽阻尼涂料的玻璃化转变温度范围，改善阻尼涂料的减振降噪性能。也就是说，羟基磷灰石超长纳米线与阻尼涂料复合可同时提高阻尼涂料的力学性能、阻燃性能和阻尼性能，并且可以改善阻尼涂料的白度和减振降噪性能。The invention adopts the flame-retardant raw material hydroxyapatite ultra-long nanowires with good biocompatibility, environmental friendliness and excellent flame-retardant performance and damping coating as raw materials, and obtains the flame-retardant ultra-long hydroxyapatite nanowire through compounding. Nanowire composite flame retardant damping coating. In the present invention, the hydroxyapatite ultra-long nanowires are high-temperature-resistant and non-combustible, and can improve the flame-retardant performance of the composite flame-retardant damping coating after being combined with the damping coating. Moreover, the hydroxyapatite ultralong nanowire has a unique one-dimensional ultralong nanostructure, which can improve the mechanical properties of the damping coating. Hydroxyapatite is an important biomaterial with good biocompatibility, environmental friendliness and excellent white color, which can improve the whiteness of damping coatings. In addition, the combination of hydroxyapatite ultra-long nanowires and damping coatings can broaden the glass transition temperature range of damping coatings and improve the vibration and noise reduction performance of damping coatings. That is to say, the combination of hydroxyapatite ultra-long nanowires and damping coating can simultaneously improve the mechanical properties, flame retardancy and damping properties of the damping coating, and can improve the whiteness and vibration and noise reduction performance of the damping coating.
所述原料中阻尼涂料可以采用任何一种商品化的阻尼涂料。Any commercially available damping paint can be used as the damping paint in the raw material.
本发明中，所述羟基磷灰石超长纳米线的长径比大于300。In the present invention, the aspect ratio of the hydroxyapatite ultra-long nanowires is greater than 300.
较佳地，所述羟基磷灰石超长纳米线的长径比大于800。Preferably, the aspect ratio of the hydroxyapatite ultra-long nanowires is greater than 800.
较佳地，所述羟基磷灰石超长纳米线可以由水热法、溶剂热法、微波加热法制备得到。Preferably, the ultra-long hydroxyapatite nanowires can be prepared by hydrothermal method, solvothermal method and microwave heating method.
本发明将羟基磷灰石超长纳米线和阻尼涂料复合制备阻燃阻尼涂料，不需要复杂的工艺和设备就能制备性能优异的阻燃阻尼涂料，具有环境友好、制备工艺简便、可以批量制备等优点。In the invention, the flame-retardant damping coating is prepared by compounding the ultra-long nanowires of hydroxyapatite and the damping coating, and the flame-retardant damping coating with excellent performance can be prepared without complex processes and equipment, and is environment-friendly, simple and convenient in the preparation process, and can be prepared in batches Etc.
本发明还提供所述羟基磷灰石超长纳米线复合阻燃阻尼涂料在机械设备领域中的应用，尤其在包括飞机、轨道列车、汽车和船舶等在内的交通机械设备领域中的应用。本发明提供的羟基磷灰石超长纳米线复合阻燃阻尼涂料具有阻燃、力学增强、减振和降噪等效果，在飞机、轨道列车、汽车和船舶等多个领域具有良好的应用前景。The present invention also provides the application of the hydroxyapatite ultra-long nanowire composite flame-retardant damping coating in the field of mechanical equipment, especially in the field of transportation machinery and equipment including airplanes, rail trains, automobiles and ships. The hydroxyapatite ultra-long nanowire composite flame-retardant damping coating provided by the present invention has the effects of flame retardancy, mechanical enhancement, vibration reduction and noise reduction, and has good application prospects in many fields such as aircraft, rail trains, automobiles and ships. .
附图说明Description of drawings
图1为羟基磷灰石超长纳米线的扫描电子显微图，该图显示多个纳米线自组装形成束状结构；Figure 1 is a scanning electron micrograph of ultra-long nanowires of hydroxyapatite, which shows that multiple nanowires self-assemble to form a bundle structure;
图2为羟基磷灰石超长纳米线的透射电子显微图。Figure 2 is a transmission electron micrograph of hydroxyapatite ultralong nanowires.
具体实施方式detailed description
以下结合附图和下述实施方式进一步说明本发明，应理解，附图及下述实施方式仅用于说明本发明，而非限制本发明。The present invention will be further described below in conjunction with the drawings and the following embodiments. It should be understood that the drawings and the following embodiments are only used to illustrate the present invention rather than limit the present invention.
本发明涉及一种具有阻燃性能的羟基磷灰石超长纳米线复合阻燃阻尼涂料，该复合阻燃阻尼涂料采用羟基磷灰石超长纳米线和阻尼涂料为原料复合配制而成，羟基磷灰石超长纳米线与阻尼涂料复合可同时提高阻尼涂料的力学性能、阻燃性能和阻尼性能，并且可以改善阻尼涂料的白度和减振降噪性能。本发明中，可以将羟基磷灰石超长纳米线与水和/或醇(包括甲醇、乙醇、丙醇和/或丁醇)混合制备成羟基磷灰石超长纳米线浆料，按照一定比例，将羟基磷灰石超长纳米线浆料和阻尼涂料混合，搅拌均匀，制备得到羟基磷灰石超长纳米线复合阻燃阻尼涂料；也可以按照一定比例直接将羟基磷灰石超长纳米线粉体与阻尼涂料混合，搅拌均匀，制备得到羟基磷灰石超长纳米线复合阻燃阻尼涂料。The invention relates to a hydroxyapatite ultra-long nanowire composite flame-retardant damping coating with flame-retardant properties. Combining the ultra-long apatite nanowires with the damping coating can simultaneously improve the mechanical properties, flame retardancy and damping properties of the damping coating, and can improve the whiteness and vibration and noise reduction performance of the damping coating. In the present invention, hydroxyapatite ultra-long nanowires can be mixed with water and/or alcohol (including methanol, ethanol, propanol and/or butanol) to prepare hydroxyapatite ultra-long nanowire slurry, according to a certain ratio , mix the hydroxyapatite ultra-long nanowire slurry and the damping coating, and stir evenly to prepare the hydroxyapatite ultra-long nanowire composite flame-retardant damping coating; it is also possible to directly mix the hydroxyapatite ultra-long nanowire The wire powder is mixed with the damping coating and stirred evenly to prepare the hydroxyapatite ultra-long nanowire composite flame-retardant damping coating.
本发明中，对作为原料的阻尼涂料没有特别限定，可以采用任何一种商品化的阻尼涂料。在本实施方式中，优选的阻尼涂料可以采用商品化的水基阻尼涂料。In the present invention, the damping paint used as a raw material is not particularly limited, and any commercially available damping paint can be used. In this embodiment, the preferred damping paint can be a commercially available water-based damping paint.
本发明中，羟基磷灰石超长纳米线的长度为10～1000微米，优选200～1000微米；单个羟基磷灰石超长纳米线的直径为5～100纳米，优选10～50纳米；纳米线的长径比大于300，优选的长径比大于800。羟基磷灰石超长纳米线具有独特的一维超长纳米结构，可以自组装形成三维网络结构，对阻尼涂料具有力学增强的作用，可以改善阻尼涂料的力学性能。In the present invention, the length of the hydroxyapatite ultra-long nanowire is 10-1000 microns, preferably 200-1000 microns; the diameter of a single hydroxyapatite ultra-long nano-wire is 5-100 nanometers, preferably 10-50 nanometers; The aspect ratio of the wire is greater than 300, preferably greater than 800. The hydroxyapatite ultra-long nanowire has a unique one-dimensional ultra-long nanostructure, which can be self-assembled to form a three-dimensional network structure, which has a mechanical enhancement effect on the damping coating and can improve the mechanical properties of the damping coating.
羟基磷灰石超长纳米线在羟基磷灰石超长纳米线复合阻燃阻尼涂料中的重量百分比含量在1～50wt.％范围内可调，本实施方式中，优选羟基磷灰石超长纳米线的重量百分比含量在5～25wt.％。当羟基磷灰石超长纳米线的重量百分比含量少于1％时，阻燃性能不佳。当羟基磷灰石超长纳米线的重量百分比含量超过50％时，干燥后涂料易变脆。The weight percent content of hydroxyapatite ultra-long nanowires in the hydroxyapatite ultra-long nanowire composite flame-retardant damping coating can be adjusted within the range of 1 to 50wt.%. In this embodiment, the preferred hydroxyapatite ultra-long The weight percent content of the nanowires is 5-25wt.%. When the weight percent content of hydroxyapatite ultra-long nanowires is less than 1%, the flame retardancy is not good. When the weight percentage of the hydroxyapatite ultra-long nanowire exceeds 50%, the coating tends to become brittle after drying.
羟基磷灰石是一种重要的生物材料，具有良好的生物相容性，环境友好，呈现优良的白色可以改善阻尼涂料的白度；羟基磷灰石超长纳米线耐高温、不燃烧，可以提高阻尼涂料的阻燃性能；羟基磷灰石超长纳米线具有独特的一维超长纳米结构，可以改善阻尼涂料的力学性能。此外，羟基磷灰石超长纳米线与阻尼涂料的复合可以拓宽阻尼涂料的玻璃化转变温度范围，改善阻尼涂料的减振降噪性能。也就是说，羟基磷灰石超长纳米线与阻尼涂料复合可同时提高阻尼涂料的力学性能、阻燃性能和阻尼性能，并且可以改善阻尼涂料的白度和减振降噪性能。Hydroxyapatite is an important biological material with good biocompatibility and environmental friendliness. It exhibits excellent white color and can improve the whiteness of damping coatings; hydroxyapatite ultra-long nanowires are high temperature resistant, non-combustible, and can Improve the flame retardancy of damping coatings; hydroxyapatite ultra-long nanowires have a unique one-dimensional ultra-long nanostructure, which can improve the mechanical properties of damping coatings. In addition, the combination of hydroxyapatite ultra-long nanowires and damping coatings can broaden the glass transition temperature range of damping coatings and improve the vibration and noise reduction performance of damping coatings. That is to say, the combination of hydroxyapatite ultra-long nanowires and damping coating can simultaneously improve the mechanical properties, flame retardancy and damping properties of the damping coating, and can improve the whiteness and vibration and noise reduction performance of the damping coating.
本发明中，羟基磷灰石超长纳米线可以由水热法、溶剂热法、微波加热法制备得到。In the present invention, the hydroxyapatite ultra-long nanowires can be prepared by a hydrothermal method, a solvothermal method, or a microwave heating method.
具体的，作为一个示例，溶剂热法制备羟基磷灰石超长纳米线可以参考发明专利“高柔韧性耐高温不燃的羟基磷灰石纸及其制备方法”(专利号：ZL201310687363.2)。Specifically, as an example, the preparation of ultra-long hydroxyapatite nanowires by solvothermal method can refer to the invention patent "high flexibility, high temperature and non-combustible hydroxyapatite paper and its preparation method" (patent number: ZL201310687363.2).
本发明中，可以将羟基磷灰石超长纳米线与水和/或醇(包括甲醇、乙醇、丙醇和/或丁醇)混合制备成羟基磷灰石超长纳米线浆料，按照一定比例，将羟基磷灰石超长纳米线浆料和阻尼涂料混合，搅拌均匀，制备得到羟基磷灰石超长纳米线复合阻燃阻尼涂料；也可以按照一定比例直接将羟基磷灰石超长纳米线粉体与阻尼涂料混合，搅拌均匀，制备得到羟基磷灰石超长纳米线复合阻燃阻尼涂料。In the present invention, hydroxyapatite ultra-long nanowires can be mixed with water and/or alcohol (including methanol, ethanol, propanol and/or butanol) to prepare hydroxyapatite ultra-long nanowire slurry, according to a certain ratio , mix the hydroxyapatite ultra-long nanowire slurry and the damping coating, and stir evenly to prepare the hydroxyapatite ultra-long nanowire composite flame-retardant damping coating; it is also possible to directly mix the hydroxyapatite ultra-long nanowire The wire powder is mixed with the damping coating and stirred evenly to prepare the hydroxyapatite ultra-long nanowire composite flame-retardant damping coating.
一方面，采用羟基磷灰石超长纳米线与水和/或醇(包括甲醇、乙醇、丙醇和/或丁醇)混合制备成羟基磷灰石超长纳米线浆料，按照一定比例，将羟基磷灰石超长纳米线浆料和阻尼涂料混合，搅拌均匀，制备得到羟基磷灰石超长纳米线复合阻燃阻尼涂料的方法时，羟基磷灰石超长纳米线与水和/或醇(包括甲醇、乙醇、丙醇和/或丁醇)的重量比例可以设为1：100～100：1，该比例范围内得到的羟基磷灰石超长纳米线浆料可以与阻尼涂料进行较好的复合。羟基磷灰石超长纳米线浆料与阻尼涂料的比例可以设为1：100～100：1。羟基磷灰石超长纳米线浆料与阻尼涂料的比例低于1：100时，阻燃性能不佳；羟基磷灰石超长纳米线浆料与阻尼涂料的比例高于100：1时，干燥后涂料易变脆。关于搅拌方式，没有特别限定，本实施方式中，优选采用机械搅拌和磁力搅拌的搅拌方式。On the one hand, hydroxyapatite ultra-long nanowire slurry is prepared by mixing hydroxyapatite ultra-long nanowires with water and/or alcohol (including methanol, ethanol, propanol and/or butanol). According to a certain proportion, the When the hydroxyapatite ultra-long nanowire slurry is mixed with the damping coating and stirred evenly to prepare the composite flame-retardant damping coating of the hydroxyapatite ultra-long nano-wire, the hydroxyapatite ultra-long nano-wire is mixed with water and/or The weight ratio of alcohol (including methanol, ethanol, propanol and/or butanol) can be set to 1:100-100:1, and the hydroxyapatite ultra-long nanowire slurry obtained in this ratio range can be compared with the damping coating. nice compound. The ratio of the hydroxyapatite ultra-long nanowire slurry to the damping coating can be set to 1:100-100:1. When the ratio of hydroxyapatite ultra-long nanowire slurry to damping coating is less than 1:100, the flame retardancy is not good; when the ratio of hydroxyapatite ultra-long nanowire slurry to damping coating is higher than 100:1, Coatings tend to become brittle after drying. The stirring method is not particularly limited, but in the present embodiment, a stirring method of mechanical stirring and magnetic stirring is preferably used.
另一方面，采用按照一定比例直接将羟基磷灰石超长纳米线粉体与阻尼涂料混合，搅拌均匀，制备得到羟基磷灰石超长纳米线复合阻燃阻尼涂料的方法时，羟基磷灰石超长纳米线粉体与阻尼涂料的比例可以设为1：100～1：4。羟基磷灰石超长纳米线粉体与阻尼涂料直接混合可以更加简化制备过程。On the other hand, when the method of directly mixing the hydroxyapatite superlong nanowire powder with the damping coating according to a certain proportion and stirring evenly to prepare the hydroxyapatite superlong nanowire composite flame-retardant damping coating, the hydroxyapatite The ratio of stone ultra-long nanowire powder to damping coating can be set to 1:100～1:4. The direct mixing of hydroxyapatite ultra-long nanowire powder and damping coating can simplify the preparation process more.
此外，本发明的羟基磷灰石超长纳米线复合阻燃阻尼涂料中，除阻尼涂料和羟基磷灰石超长纳米线以外，还可以含有阻燃阻尼涂料领域中公知的各种添加剂。该添加剂没有特别限定。In addition, the hydroxyapatite ultra-long nanowire composite flame-retardant damping coating of the present invention may contain various additives known in the field of flame-retardant damping coatings in addition to the damping coating and hydroxyapatite ultra-long nanowires. The additive is not particularly limited.
本发明提供的羟基磷灰石超长纳米线复合阻燃阻尼涂料具有阻燃、力学增强、减振和降噪等效果，在飞机、轨道列车、汽车和船舶等多个领域具有良好的应用前景。The hydroxyapatite ultra-long nanowire composite flame-retardant damping coating provided by the present invention has the effects of flame retardancy, mechanical enhancement, vibration reduction and noise reduction, and has good application prospects in many fields such as aircraft, rail trains, automobiles and ships. .
本发明的有益效果在于：The beneficial effects of the present invention are:
本发明将羟基磷灰石超长纳米线和阻尼涂料复合制备阻燃阻尼涂料，具有环境友好、制备工艺简便、可以批量制备等优点；In the invention, the flame retardant damping coating is prepared by compounding the ultra-long hydroxyapatite nanowire and the damping coating, which has the advantages of being environmentally friendly, simple and convenient preparation process, and can be prepared in batches;
本发明采用的羟基磷灰石超长纳米线呈优质的白色，可以改善涂料的白度；The ultra-long nanowires of hydroxyapatite used in the present invention are high-quality white, which can improve the whiteness of the paint;
本发明采用的羟基磷灰石超长纳米线具有超长一维纳米结构，可以改善阻尼涂料的力学性能；The hydroxyapatite ultra-long nanowires adopted in the present invention have an ultra-long one-dimensional nanostructure, which can improve the mechanical properties of the damping coating;
本发明采用的羟基磷灰石超长纳米线耐高温、不燃烧，可以提高阻尼涂料的阻燃性能；The hydroxyapatite ultra-long nanowires adopted in the present invention are resistant to high temperature and non-combustible, and can improve the flame-retardant performance of the damping coating;
羟基磷灰石超长纳米线与阻尼涂料的复合可以拓宽阻尼涂料的玻璃化转变温度范围，改善阻尼涂料的减振降噪性能；The combination of hydroxyapatite ultra-long nanowires and damping coating can broaden the glass transition temperature range of damping coating and improve the vibration and noise reduction performance of damping coating;
本发明提供的羟基磷灰石超长纳米线复合阻燃阻尼涂料具有阻燃、力学增强、减振和降噪等效果，在飞机、轨道列车、汽车和船舶等多个领域具有良好的应用前景。The hydroxyapatite ultra-long nanowire composite flame-retardant damping coating provided by the present invention has the effects of flame retardancy, mechanical enhancement, vibration reduction and noise reduction, and has good application prospects in many fields such as aircraft, rail trains, automobiles and ships. .
下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。Examples are given below to describe the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention, and should not be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art according to the above contents of the present invention all belong to the present invention scope of protection. The specific process parameters and the like in the following examples are only examples of suitable ranges, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not limited to the specific values exemplified below.
实施例1Example 1
采用水做溶剂配制固体含量为50％的羟基磷灰石超长纳米线浆料。按照羟基磷灰石超长纳米线和德国汉高阻尼涂料重量比为1：20的配方，将羟基磷灰石超长纳米线和阻尼涂料混合，机械搅拌均匀。得到羟基磷灰石超长纳米线复合阻燃阻尼涂料。The hydroxyapatite ultra-long nanowire slurry with a solid content of 50% is prepared by using water as a solvent. According to the formula that the weight ratio of hydroxyapatite ultra-long nanowires and German Henkel damping coating is 1:20, the hydroxyapatite ultra-long nanowires and damping coating are mixed and mechanically stirred evenly. The hydroxyapatite ultra-long nanowire composite flame-retardant damping coating is obtained.
玻璃化转变温度范围测试：采用差示扫描量热分析法测定阻燃阻尼涂料的玻璃化转变温度范围。加入5wt.％的羟基磷灰石超长纳米线的阻尼涂料，其玻璃化转变温度范围约为87.6～173.6℃。在阻燃实验中，观察到有一定程度的燃烧，但产生的烟雾明显减少，即加入少量羟基磷灰石纳米线后，阻尼涂料的阻燃性能有所提高。Glass transition temperature range test: The glass transition temperature range of the flame retardant damping coating is determined by differential scanning calorimetry. Adding 5wt.% hydroxyapatite ultra-long nanowires to the damping coating, the glass transition temperature range is about 87.6-173.6°C. In the flame retardant experiment, a certain degree of combustion was observed, but the smoke produced was significantly reduced, that is, the flame retardant performance of the damping coating was improved after adding a small amount of hydroxyapatite nanowires.
实施例2Example 2
采用水做溶剂配制固体含量为50％的羟基磷灰石超长纳米线浆料。按照羟基磷灰石超长纳米线和德国汉高阻尼涂料重量比为1：10的配方，将羟基磷灰石超长纳米线和阻尼涂料混合，机械搅拌均匀。得到羟基磷灰石超长纳米线复合阻燃阻尼涂料。The hydroxyapatite ultra-long nanowire slurry with a solid content of 50% is prepared by using water as a solvent. According to the formula that the weight ratio of hydroxyapatite ultra-long nanowires and German Henkel damping coating is 1:10, the hydroxyapatite ultra-long nanowires and damping coating are mixed and mechanically stirred evenly. The hydroxyapatite ultra-long nanowire composite flame-retardant damping coating is obtained.
玻璃化转变温度范围测试：采用差示扫描量热分析法测定阻燃阻尼涂料的玻璃化转变温度范围。加入10wt.％的羟基磷灰石超长纳米线的阻尼涂料，其玻璃化转变温度范围约为86.4～177.2℃。在阻燃实验中，未观察到燃烧现象，并且未观察到烟雾产生，即加入10wt.％的羟基磷灰石纳米线后，阻尼涂料的阻燃性能显著提高。Glass transition temperature range test: The glass transition temperature range of the flame retardant damping coating is determined by differential scanning calorimetry. Adding 10wt.% of hydroxyapatite ultra-long nanowires to the damping coating has a glass transition temperature range of about 86.4-177.2°C. In the flame retardant experiment, no burning phenomenon was observed, and no smoke generation was observed, that is, after adding 10wt.% of hydroxyapatite nanowires, the flame retardant performance of the damping coating was significantly improved.
实施例3Example 3
采用水做溶剂配制固体含量为50％的羟基磷灰石超长纳米线浆料。按照羟基磷灰石超长纳米线和德国汉高阻尼涂料重量比为1：4的配方，将羟基磷灰石超长纳米线和阻尼涂料混合，机械搅拌均匀。得到羟基磷灰石超长纳米线复合阻燃阻尼涂料。The hydroxyapatite ultra-long nanowire slurry with a solid content of 50% is prepared by using water as a solvent. According to the formula that the weight ratio of hydroxyapatite ultra-long nanowires and German Henkel damping coating is 1:4, the hydroxyapatite ultra-long nanowires and damping coating are mixed and mechanically stirred evenly. The hydroxyapatite ultra-long nanowire composite flame-retardant damping coating is obtained.
玻璃化转变温度范围测试：采用差示扫描量热分析法测定阻燃阻尼涂料的玻璃化转变温度范围。加入25wt.％的羟基磷灰石超长纳米线的阻尼涂料，其玻璃化转变温度范围约为55.4～197.6℃。在阻燃实验中，未观察到燃烧现象，而且未观察到烟雾产生，即加入25wt.％的羟基磷灰石纳米线后，阻尼涂料具有优异的阻燃性能。Glass transition temperature range test: The glass transition temperature range of the flame retardant damping coating is determined by differential scanning calorimetry. Adding 25wt.% of hydroxyapatite ultra-long nanowires to the damping coating has a glass transition temperature range of about 55.4-197.6°C. In the flame retardant experiment, no burning phenomenon was observed, and no smoke generation was observed, that is, after adding 25wt.% of hydroxyapatite nanowires, the damping coating has excellent flame retardant performance.
实施例4Example 4
采用水做溶剂配制固体含量为50％的羟基磷灰石超长纳米线浆料。按照羟基磷灰石超长纳米线和德国汉高阻尼涂料重量比为1：2的配方，将羟基磷灰石超长纳米线和阻尼涂料混合，机械搅拌均匀。得到羟基磷灰石超长纳米线复合阻燃阻尼涂料。The hydroxyapatite ultra-long nanowire slurry with a solid content of 50% is prepared by using water as a solvent. According to the formula that the weight ratio of hydroxyapatite ultra-long nanowires and German Henkel damping coating is 1:2, the hydroxyapatite ultra-long nanowires and damping coating are mixed and mechanically stirred evenly. The hydroxyapatite ultra-long nanowire composite flame-retardant damping coating is obtained.
玻璃化转变温度范围测试：采用差示扫描量热分析法测定阻燃阻尼涂料的玻璃化转变温度范围。加入50wt.％的羟基磷灰石超长纳米线的阻尼涂料，其玻璃化转变温度范围约为40.1～233.1℃。在阻燃实验中，未观察到燃烧现象，而且未观察到烟雾产生，即加入50wt.％的羟基磷灰石纳米线后，阻尼涂料具有更加优异的阻燃性能。Glass transition temperature range test: The glass transition temperature range of the flame retardant damping coating is determined by differential scanning calorimetry. Adding 50wt.% hydroxyapatite ultra-long nanowires to the damping coating, the glass transition temperature range is about 40.1-233.1°C. In the flame retardant experiment, no burning phenomenon was observed, and no smoke generation was observed, that is, after adding 50wt.% of hydroxyapatite nanowires, the damping coating has more excellent flame retardant performance.
图1为羟基磷灰石超长纳米线的扫描电子显微图，该图显示多个纳米线自组装形成束状结构；图2为羟基磷灰石超长纳米线的透射电子显微图。由图1、图2可知产物羟基磷灰石为超长纳米线，长度200微米以上，羟基磷灰石超长纳米线的直径约为10至几十纳米。Figure 1 is a scanning electron micrograph of hydroxyapatite ultra-long nanowires, which shows that multiple nanowires self-assemble to form a bundle structure; Figure 2 is a transmission electron micrograph of hydroxyapatite ultra-long nanowires. It can be seen from Figures 1 and 2 that the product hydroxyapatite is an ultra-long nanowire with a length of more than 200 microns, and the diameter of the hydroxyapatite ultra-long nanowire is about 10 to tens of nanometers.
产业应用性：本发明所用阻燃原料羟基磷灰石超长纳米线生物相容性好、环境友好、制备工艺简单、易于实现批量生产。本发明提供的羟基磷灰石超长纳米线复合阻燃阻尼涂料具有良好的力学性能、阻燃性能和减振降噪效果，在飞机、轨道列车、汽车和船舶等多个领域具有良好的应用前景。Industrial applicability: the flame-retardant raw material hydroxyapatite ultra-long nanowire used in the present invention has good biocompatibility, environmental friendliness, simple preparation process and easy mass production. The hydroxyapatite ultra-long nanowire composite flame-retardant and damping coating provided by the present invention has good mechanical properties, flame-retardant properties, and vibration and noise reduction effects, and has good applications in many fields such as aircraft, rail trains, automobiles, and ships. prospect.
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| CN107686549A (en) * | 2017-08-29 | 2018-02-13 | 华南理工大学 | A kind of high performance polyurethane and preparation method and application |
| CN114426702A (en) * | 2022-01-19 | 2022-05-03 | 江西广源化工有限责任公司 | Composite inorganic flame retardant and preparation method thereof |
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| CN107686549B (en) * | 2017-08-29 | 2020-05-22 | 华南理工大学 | High-performance polyurethane and preparation method and application thereof |
| CN114426702A (en) * | 2022-01-19 | 2022-05-03 | 江西广源化工有限责任公司 | Composite inorganic flame retardant and preparation method thereof |
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