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高密度聚乙烯基木塑复合材料阻燃性能的研究

Study on Flame Retardancy of Wood Plastic Based HDPE Composites

【作者】 黄涛

【导师】 雷文;

【作者基本信息】 南京林业大学 , 材料学, 2012, 硕士

【摘要】 随着高分子材料应用范围的日益扩大,特别是木塑复合材料(WPC)的在国内应用领域的快速扩展,其安全性愈加受到重视。但是由于它属于易燃材料,极大的限制了WPC的应用范围。这也凸显了复合材料阻燃研究的重要性。本论文对阻燃剂及发展趋势作了详细的介绍;并合成低毒、低害、阻燃效果好的三位一体复合型膨胀阻燃剂,对其进行残炭率、膨胀度、红外表征及热重分析,确定其最佳合成参数;并把合成的阻燃剂用于杨木薄板以及WPC的阻燃处理,以此来研究阻燃剂添加方式及阻燃剂的添加量对WPC燃烧和力学性能的影响;作为对比,最后研究了溴系阻燃体系对WPC的性能影响。本论文的主要研究结果如下:1.采用不同方法合成阻燃剂,并取得了良好的阻燃效果。膨胀阻燃剂a(IFR-a)是磷酸、季戊四醇与苯胺在摩尔比为2:1:1、反应温度100℃、反应时间6h条件下制备的阻燃剂,该阻燃剂有着最好的膨胀性。膨胀阻燃剂b(IFR-b)则是磷酸、季戊四醇与苯胺的摩尔比为2:1:2、反应温度100℃、反应时间6h条件下制备的阻燃剂。两种阻燃剂的性能不尽相同,其中IFR-a的膨胀性很好,IFR-b残炭率很高。经过膨胀测试后,IFR-a炭层薄且上面有很多小气孔,IFR-b炭层厚且致密,两者的阻燃机理不同;通过热重分析可得出IFR-b比IFR-a的热稳定性好。2.用IFR-a对杨木薄板进行阻燃浸渍处理,浸渍温度对杨木薄板的载药量和失重率影响最大,浸渍浓度其次,浸渍时间影响最小。通过正交实验可得出杨木薄板的最佳浸渍工艺为:浸渍温度80℃,阻燃剂浓度18%,浸渍时间为3h。利用最佳浸渍工艺条件制成的样品10,氧指数可达46.7%。3.合成的阻燃剂的添加方式对WPC的热降解温度影响不大。无论以何种方式将阻燃剂加入到材料中,与未阻燃的WPC相比,复合材料中木粉的热分解都会提前发生,HDPE的质量损失减少。采用阻燃剂浸渍处理木粉制成的WPC与直接添加阻燃剂的WPC相比,前者的阻燃性能虽比不上后者,但是其力学性能下降比后者少。4.随着阻燃剂含量的增加,WPC燃烧后表面膨胀得就越大,炭层和膨胀度更加趋向致密和稳定,从而使其阻燃作用更强,LOI值更高。200g的WPC中加入40g阻燃剂时,垂直燃烧可达到FV-2级,并且无滴落;当200g的WPC中加入60g阻燃剂时,垂直燃烧可达到FV-0级,氧指数为28.2%。5.十溴联苯醚(DBDTO)单独用作阻燃剂处理材料时,阻燃效果不佳,三氧化二锑(Sb2O3)的加入会改善材料的阻燃性能和力学性能。DBDTO/Sb2O3在WPC最佳配比为3:12:1。

【Abstract】 As a sustainable green material, the wood plastic composites(WPC)are widely usednowadays. However the further application is restricted due to its flammability. Therefore, it isimportant to study on the flame retardancy of the WPC.In this paper, the flame-retardant mechanism, application of major flame retardants wereintroduced and a low toxicity, less harmful and good effect of trinity intrumescent flame retardant(IFR) was synthesized. The effects of the IFR content and added methods on flame retardancy ofwood flour based highdensity polyethylene composites (HDPE-Wood) were studied. Forcomparison, flame retarded WPC were also prepared with decabromodiphenyl oxide (DBDPO)and antimonous oxide (Sb2O3). The flame retardancy and mechanical properties of flameretarded WPC were studied by thermalgravimereic analysis (TG), limited oxygen index (LOI),vertical firing test.In this paper, the main research conclusions are as follows:1. The flame retardants synthesized with two different methods, which have a good flameretardantcy effect. IFR-a which had the best expansion performance was synthesized byphosphoric acid, pentaerythritol and aniline, the molar ratio was2:1:1, reaction temperature was100℃and reaction time was6h. IFR-b was synthesized by phosphoric acid, pentaerythritol andaniline, the molar ratio was2:1:2, reaction temperature was100℃and reaction time was6h.According to the char yield test, the char layer of IFR-a had lots of small holes, whereas the charlayer of IFR-b was thick and compact. It is expected that the mechanisms of the flame retardantswere different. From the TG test, it is suggested that the IFR-b had the better thermal stabilitythan IFR-a.2. Poplar thin board treated by IFR-a solution was also studied. It is clear that the soakingtemperature was the crucial factor. By orthogonal experiment the best wood fire-retardanttreatment conditions were found: soaking temperature was80℃, IFR contration was8%, soakingtime was3h. The LOI of the sample10made according to the optimal treatment conditions canreach as high as46.7%.3. It could be observed that there was no significantly influence on the thermal stabilitywhen WPC treated by different methods. Compared with nonflame retarded WPC, the woodflour thermal decomposition of flame retarded WPC will occur in advance, while the mass loss ofHDPE will decrease. The WPC made with the wood flour treated by IFR solution had the lessflame retardancy than the WPC made with the IFR filled directly, whereas the former WPC hadthe better mechanical properties. 4. With the increase of IFR content, the surface of WPC expansion became bigger after0burning, as well as the char layer became more dense and stable. As mentioned above, it wasfound that the flame retardancy was better. When added40g IFR into200g WPC, the verticalfiring rating can achieve FV-2and no dripings; when added60g IFR into200g WPC, the verticalfiring rating can reach FV-0, the LOI was28.2%.5. It is showed that there was no significantly influence on flame retardancy when theDBDPO added to the WPC alone. The flame retardancy and mechanical properties will improveas the added of Sb2O3. The WPC will have the best flame retardancy when DBDPO and Sb2O3have the weight ratio of3:12:1.

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