微胶囊阻燃剂的制备及其在PVC膜结构材料中应用研究

发布时间：2018-01-16 00:22

本文关键词：微胶囊阻燃剂的制备及其在PVC膜结构材料中应用研究　出处：《浙江理工大学》2017年硕士论文　论文类型：学位论文

【摘要】：PVC膜结构材料是以高强织物例如涤纶织物等为骨架,两面均匀涂覆聚氯乙烯涂层材料,具有成本低廉、韧性优良,易加工等优点,而被广泛应用在建筑、运动、休闲等领域。一般柔性PVC涂层膜材料加工过程中需加入大量增塑剂(60%以上)以提高柔软度和改善样品的加工性能,而增塑剂一般为易燃物,这不仅大幅度降低PVC膜材料的阻燃性能,而且也会限制此类材料的广泛应用。柔性PVC膜材料在燃烧的过程中会放出大量有毒有害黑烟,威胁人类生命安全,因此对于PVC的阻燃消烟的研究具有重要意义。为了降低材料的潜在火灾危害,需要研发一种“绿色环保”高效阻燃抑烟剂来满足材料阻燃要求。研究发现锡类化合物例如锡酸锌(ZnSnO3)可以作为含卤聚合物材料的高效阻燃抑烟剂,其添加量仅为5%~10%,但其在基体中分散性较差且成本较高,因此应用受到限制。为了提高ZnSnO3阻燃效率及其在聚合物基体中的分散性,同时又降低阻燃剂使用成本,将氢氧化镁(MTH)包覆ZnSnO3和三聚氰胺甲醛树脂(MF)与MTH双层包覆ZnSnO3,组成镁-锡-锌、氮-镁-锡-锌协同阻燃体系,是一种切实可行的方法。本课题首先选用绿色环保的锡酸锌(ZS)为芯材料,以氢氧化镁和三聚氰胺甲醛树脂作为囊材,采用化学沉淀法和原位聚合法制备单层和双层微胶囊阻燃剂。利用傅里叶红外光谱、X射线粉末衍射仪(XRD)、透射电镜(TEM)、场发射扫描电镜(SEM)、热重分析(TGA)等方法对其进行了一系列表征。其结果显示制备的单层和双层微胶囊阻燃剂粒径为50nm~250nm,具有核壳分层结构,其热稳定性也发生了变化。将制备的微胶囊阻燃剂通过机械搅拌法加入PVC浆料制备阻燃PVC膜材料,采用垂直水平燃烧法,极限氧指数法(LOI),烟密度测试(SDR),热重分析(TGA),扫描电镜(SEM)等方法测试了其阻燃抑烟性能,结果表明微胶囊阻燃剂添加量8%左右,即可使PVC膜材料的LOI值提高至27%以上,同时在垂直水平燃烧测试中,燃烧剩余长度大幅增加,烟密度下降至50%以下,表现出优异的阻燃抑烟性能。最后通过扫描电镜、拉伸性能测试和旋转流变仪研究了微胶囊阻燃剂在基体中分布情况和其对基体机械性能的影响。研究结果显示相较于纯氢氧化镁和锡酸锌等无机阻燃剂在基体中的分布情况,经过三聚氰胺甲醛树脂包覆的双层微胶囊阻燃剂在基体中分布更均匀,团聚现象较少,表现出更佳的分散性。同时双层微胶囊阻燃剂对于基体机械性能影响程度较小于前述无机阻燃剂,表现出和基体更好的相容性。双层微胶囊在PVC浆料中对其黏度影响程度最小,不会大幅度增加PVC浆料黏度,对生产加工工艺的影响较小,增加了后期应用范围。
[Abstract]:PVC membrane structure material is based on high strength fabric such as polyester fabric and evenly coated with PVC coating material on both sides. It has the advantages of low cost, good toughness and easy processing, so it is widely used in construction. Sports, leisure and other fields. In general, flexible PVC coating film materials need to add a large amount of plasticizer more than 60%) in order to improve the softness and improve the processing performance of the sample, while the plasticizer is generally flammable. This will not only greatly reduce the flame retardancy of PVC membrane materials, but also limit the wide application of these materials. Flexible PVC membrane materials will emit a large number of toxic and harmful black smoke during combustion. As a threat to human life and safety, it is of great significance to study the flame retardancy and smoke suppression of PVC, in order to reduce the potential fire hazards of materials. It is necessary to develop a kind of "green environmental protection" high efficiency flame retardant and smoke suppressant to meet the requirements of material flame retardancy. It has been found that tin compounds such as zinc stearate ZnSnO _ 3). It can be used as an effective flame retardant and smoke suppressant for halogenated polymer materials. The addition amount of ZnSnO3 is only 5 / 10, but its dispersion in the matrix is poor and the cost is high, so its application is limited. In order to improve the flame retardant efficiency of ZnSnO3 and its dispersity in polymer matrix. At the same time, the use cost of flame retardant was reduced. Magnesium hydroxide and melamine formaldehyde resin were coated with ZnSnO3 and melamine formaldehyde resin respectively. ZnSnO _ 3 was coated with MTH to form magnesia-tin zinc. Nitrogen-magnesium-tin zinc synergistic flame-retardant system is a feasible method. First of all, the green zinc stearate ZSs is chosen as the core material, and magnesium hydroxide and melamine formaldehyde resin are used as the capsule materials. Monolayer and double-layer microcapsule flame retardants were prepared by chemical precipitation and in situ polymerization. Field emission scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and other methods were used to characterize the flame retardants. The results showed that the diameter of the prepared flame retardants was 50 nm. The microcapsule flame retardant was added into the PVC slurry by mechanical stirring method to prepare the flame retardant PVC membrane material, and the vertical horizontal combustion method was adopted. The flame retardancy and smoke inhibition were tested by limiting oxygen index (LO) method, smoke density test (SDR), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The results show that the LOI value of PVC film can be increased to more than 27% when the amount of microcapsule flame retardant is about 8%, and the residual length of combustion is increased greatly in the vertical horizontal combustion test. The smoke density decreased below 50%, showing excellent flame retardancy and smoke inhibition. Finally, scanning electron microscope was used. The distribution of microencapsulated flame retardant in matrix and its effect on the mechanical properties of the matrix were studied by tensile test and rotary rheometer. The results showed that the flame retardants such as pure magnesium hydroxide and zinc stannate were found in the matrix compared with those of inorganic flame retardants such as pure magnesium hydroxide and zinc stannate. The distribution of. The flame retardant of double-layer microcapsule coated with melamine formaldehyde resin is more evenly distributed in the matrix, and the phenomenon of agglomeration is less. At the same time, the effect of double-layer microcapsule flame retardants on the mechanical properties of the matrix is less than that of the inorganic flame retardants mentioned above. The effect of double-layer microcapsules on the viscosity of PVC slurry is the least, and the viscosity of PVC slurry will not be increased significantly, but the effect on the production and processing process is small. The range of later application is increased.
【学位授予单位】：浙江理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TS195.24

【参考文献】