配位均匀沉淀法合成纳米硼酸锌及其应用研究
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摘要
无机阻燃剂具有热稳定性好、不挥发、不析出、不产生腐蚀性和有毒气体等特点,其用量占各类阻燃剂的一半以上。硼系无机阻燃剂是一类多功能阻燃剂,近年来发展较快,其中硼酸锌是一种性能优良的环保型无机阻燃剂,它能代替氧化锑用于聚氯乙烯、聚酯、酚醛塑料、纤维织物等多种材料,是应用最广泛的阻燃剂之一。目前,该类阻燃剂以粒度超细化和分布均匀化为其发展的方向。
本论文采用“配位均匀沉淀法”研制了几种不同形貌的新型纳米硼酸锌,深入探讨和优化了制备工艺条件,采用透射电镜、X射线衍射、热重—差热分析、红外光谱、示差扫描量热分析等手段对粒子的结构及形貌进行了表征分析,并对产物进行了表面改性研究,初步探讨了纳米硼酸锌的阻燃性能。
以锌盐和硼砂为原料制备出了组成为2ZnO·2.2B_2O_3·3H_2O(ZnO%=44.31%,B_2O_3%=40.92%,H_2O%=14.77%)的新型纳米硼酸锌,产物为呈片状结构,边长大约100nm~200nm;以氧化锌和硼酸为原料,制备出了新型纤维状纳米硼酸锌ZnO·yB2O3·zH2O(y=0.3~0.4,z=1.0~1.4),产物是由直径约为15nm左右,长为数百纳米至几微米的纤维状产物交织而成的网状结构,目前在国内外文献中,未见有这种形貌纳米硼酸的相关报道。
以十二烷基苯磺酸钠作为改性剂,对产物2ZnO·2.2B_2O_3·3H_2O进行了表面改性研究。改性后的产品大大减少了纳米颗粒的团聚、增大了比表面积,产品明显由亲水性转为亲油性。
以残炭率为指标,初步研究了产物的阻燃性能。将产品添加到聚丙烯(PP)和高密度聚乙烯(HDPE)中,当其用量为树脂质量的12%左右时,其残炭率均可达65%左右,显示了优良的阻燃抑烟性能,且效果远远优于市售ZB2335。当添加到低密度聚乙烯中,测试结果显示,与市售ZB2335相比,产物对低密度聚乙烯(LDPE)的力学性能也有所改善。
Inorganic flame retardant has become the goal of flame retardant beacanse of its fine property. Moreover, their action as smoke suppressants, afterglow suppressants, corrosion inhibitors, and synergistic agent has been pointed out. Zinc borate is a new type of inorganic flame retardant, which is also a series of compound of B and Zn oxide. Previous studies have demonstrated that they are commonly used as flame-retardant filler in PVC, PP, polyamides, epoxy resins, etc. The nano-sized particle and uniform dispersion is the trend of this kind of flame retardant.
A new method, namely, coordination homogenious precipitation method was described to synthesize nanometer zinc borate powders with different shapes. Transmission electron microscope(TEM), powder X–ray diffraction(XRD), thermal analysis(TG-DTA), infrared absorption spectroscopy(IR), differential scanning calorimetry(DSC) were used to characterize the microstructure and morphology of the products, the surface modification of the product was studied in this paper, and the application of nanometer zinc borate as flame retardant was also investigated preliminarily.
A new nano 2ZnO·2.2B_2O_3·3H_2O (ZnO%=44.31%, B2O3%=40.92%, H2O%=14.77%), was prepared via coordination homogeneous precipitation method using zinc nitrate and borax as raw materials. The product appeared to have a flake-like shape and with the particle size of around 100–200nm; and a netlike nano zinc borate ZnO·yB_2O_3·zH_2O (y=0.3~0.4, z=1.0~1.4) was prepared using zinc oxide and boric acid as raw materials, the product were composed of fibers with diameter about 15nm and length about hundreds of nanometers, some of which entangled each other to form dendritic or interconnected networks.
Surface modification of the product (2ZnO·2.2B_2O_3·3H_2O) was carried out using sodium dodecyl benzene sulfonate (SDBS) in this paper. It revealed that the zinc borate after modification transferred from hydrophilisity to lipophilicity, and the dispersion of the nanosized particles was greatly improved when they were modificated.
The pilot study revealed that the product had better char formation effect than the commercial ZB2335 when it was introduced into polypropylene (PP) and high-density polyethylene (HDPE) as flame-retardant filler. The carbon residue ratio of PP and HDPE were about 65% when the sample content was about 12wt %.
本论文采用“配位均匀沉淀法”研制了几种不同形貌的新型纳米硼酸锌,深入探讨和优化了制备工艺条件,采用透射电镜、X射线衍射、热重—差热分析、红外光谱、示差扫描量热分析等手段对粒子的结构及形貌进行了表征分析,并对产物进行了表面改性研究,初步探讨了纳米硼酸锌的阻燃性能。
以锌盐和硼砂为原料制备出了组成为2ZnO·2.2B_2O_3·3H_2O(ZnO%=44.31%,B_2O_3%=40.92%,H_2O%=14.77%)的新型纳米硼酸锌,产物为呈片状结构,边长大约100nm~200nm;以氧化锌和硼酸为原料,制备出了新型纤维状纳米硼酸锌ZnO·yB2O3·zH2O(y=0.3~0.4,z=1.0~1.4),产物是由直径约为15nm左右,长为数百纳米至几微米的纤维状产物交织而成的网状结构,目前在国内外文献中,未见有这种形貌纳米硼酸的相关报道。
以十二烷基苯磺酸钠作为改性剂,对产物2ZnO·2.2B_2O_3·3H_2O进行了表面改性研究。改性后的产品大大减少了纳米颗粒的团聚、增大了比表面积,产品明显由亲水性转为亲油性。
以残炭率为指标,初步研究了产物的阻燃性能。将产品添加到聚丙烯(PP)和高密度聚乙烯(HDPE)中,当其用量为树脂质量的12%左右时,其残炭率均可达65%左右,显示了优良的阻燃抑烟性能,且效果远远优于市售ZB2335。当添加到低密度聚乙烯中,测试结果显示,与市售ZB2335相比,产物对低密度聚乙烯(LDPE)的力学性能也有所改善。
Inorganic flame retardant has become the goal of flame retardant beacanse of its fine property. Moreover, their action as smoke suppressants, afterglow suppressants, corrosion inhibitors, and synergistic agent has been pointed out. Zinc borate is a new type of inorganic flame retardant, which is also a series of compound of B and Zn oxide. Previous studies have demonstrated that they are commonly used as flame-retardant filler in PVC, PP, polyamides, epoxy resins, etc. The nano-sized particle and uniform dispersion is the trend of this kind of flame retardant.
A new method, namely, coordination homogenious precipitation method was described to synthesize nanometer zinc borate powders with different shapes. Transmission electron microscope(TEM), powder X–ray diffraction(XRD), thermal analysis(TG-DTA), infrared absorption spectroscopy(IR), differential scanning calorimetry(DSC) were used to characterize the microstructure and morphology of the products, the surface modification of the product was studied in this paper, and the application of nanometer zinc borate as flame retardant was also investigated preliminarily.
A new nano 2ZnO·2.2B_2O_3·3H_2O (ZnO%=44.31%, B2O3%=40.92%, H2O%=14.77%), was prepared via coordination homogeneous precipitation method using zinc nitrate and borax as raw materials. The product appeared to have a flake-like shape and with the particle size of around 100–200nm; and a netlike nano zinc borate ZnO·yB_2O_3·zH_2O (y=0.3~0.4, z=1.0~1.4) was prepared using zinc oxide and boric acid as raw materials, the product were composed of fibers with diameter about 15nm and length about hundreds of nanometers, some of which entangled each other to form dendritic or interconnected networks.
Surface modification of the product (2ZnO·2.2B_2O_3·3H_2O) was carried out using sodium dodecyl benzene sulfonate (SDBS) in this paper. It revealed that the zinc borate after modification transferred from hydrophilisity to lipophilicity, and the dispersion of the nanosized particles was greatly improved when they were modificated.
The pilot study revealed that the product had better char formation effect than the commercial ZB2335 when it was introduced into polypropylene (PP) and high-density polyethylene (HDPE) as flame-retardant filler. The carbon residue ratio of PP and HDPE were about 65% when the sample content was about 12wt %.
引文
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