阻燃硬质聚氨酯泡沫的抑烟减毒研究

发布时间：2018-01-31 05:40

本文关键词： 阻燃硬质聚氨酯泡沫抑烟减毒过渡金属羟基锡酸盐超支化磷氮阻燃剂　出处：《中国科学技术大学》2017年硕士论文　论文类型：学位论文

【摘要】：本论文专注于硬质聚氨酯泡沫(RPUF)燃烧毒性的研究,以经典的聚磷酸铵/二甲基膦酸二甲酯(APP/DMMP)为阻燃体系,配合实验室制备的一系列过渡金属类助剂,成功制备了多个系列的复合RPUF材料,并采用多种技术手段对其燃烧毒性进行了系统评估,初步揭示了各类助剂的抑烟减毒机理。为了改进阻燃体系对RPUF的燃烧毒性的影响,在原有传统阻燃体系的基础上,设计合成了两种超支化磷氮系阻燃剂,并将其引入到RPUF体系中。此外,为了探究两种超支化阻燃剂应用于其他基体的可能性,将其引入到聚苯二甲酸丁二醇酯(PBT)和聚丙烯(PP)中。本论文的研究工作共划分为四个部分,现简要分述如下:1)通过湿化学的方法,制备了具有规则八面体形貌的Cu_2O颗粒及其杂化物Cu_2O@CNT、Cu_2O@GO。将其引入到阻燃RPUF体系中得到复合RPUF材料。锥形量热测试表明,Cu20及其系列杂化物均使得热释放速率(HRR)和产烟速率(SPR)明显下降。烟密度箱测试表明,Cu_2O及其系列杂化物能够有效抑制APP/DMMP带来的增烟效应,而且使复合RPUF材料的产烟低于纯样品。在火灾毒性测试平台(FTTP)的测试中,825℃比650℃更能使Cu_2O发挥抑烟减毒作用。热重红外分析表明,Cu20使材料的气相逸出强度明显减弱,而且使CO的逸出速率明显降低。激光拉曼分析显示,Cu_2O及其系列杂化物使材料残炭的石墨化程度提高,可知其改变了材料热解、炭化的历程,有利于烟气的抑制。2)通过水热的方法,制备了一系列炭包裹微球Fe_20_3@C、Cu@C和Cu20@Fe_2O_3@C。将其引入阻燃RPUF体系,制得了一系列复合RPUF材料。锥形量热测试发现,三种微球都使HRR和SPR显著降低,其中Fe_20_3@C效果最佳。烟密度箱给出的结果表明,在产烟方面三种微球都在一定程度上抑制了 APP/DMMP的消极影响,但是均未能达到纯RPUF的水平。FTTP的测试发现,在650℃时无论通风状态如何,各微球都未能抑制RPUF的产烟;而通风条件不好时使CO的产率降低。热重红外分析显示,各微球都使材料的气相逸出强度下降,其中尤以Cu@C的效果最佳。拉曼分析表明,各微球也都使得材料残炭的石墨化程度提高,其中尤以Fe_2O_3@C的表现最好,可见微球对于烟气的阻隔抑制发挥了积极作用。3)采用溶液共沉淀的方法,制备了一系列形貌各异的羟基锡酸盐:羟基锡酸锌(ZHS)、羟基锡酸铜(CHS)和羟基锡酸铁(IHS)。将其引入到阻燃RPUF体系中,制备了一系列复合RPUF材料。热重分析发现,各羟基锡酸盐使RPUF的残炭明显增加,使降解温度区间变窄而初始降解提前。锥形量热仪的测试结果显示,ZHS、CHS以及IHS抑制HRR的效率都偏低,但都能够显著抑制SPR。在烟密度箱的测试中,三种羟基锡酸盐也表现出了优良的抑烟效率。FTTP的测试结果表明,在抑制产烟上三种盐均不理想,但使CO产率有了明显降低。热重红外分析表明,ZHS、CHS和IHS抑制气相产物的效率依次升高,拉曼分析也发现,IHS最能够提高材料残炭的石墨化程度。4)为了避免传统阻燃剂带来的增烟效应,自主合成了超支化磷氮系阻燃剂CEPO和HBP。将其应用到RPUF中并配合各类助剂,制得了一系列复合RPUF材料。锥形量热的测试结果显示,10份的HBP代替5份APP和5份HBP后,材料的HRR有了显著下降,SPR更是降到了接近于零的水平。烟密度箱的测试结果显示,RPUF/HBP的产烟量远低于RPUF/APP/HBP,加入Cu20、Fe_20_3@C或ZHS后,产烟又有了进一步降低。在FTTP的测试中,RPUF/10HBP的产烟已经接近纯样的水平,加入5份ZHS后光透过率已接近100%。5)为了初步探究CEPO和HBP在其他聚合物基体中的阻燃表现,将APP/CEPO体系应用于PBT中,将APP/HBP体系应用于PP中,发现两体系均具有非常高的阻燃效率,其中尤以比例为1:1时最好。热重红外分析、扫面电子显微镜(SEM)以及拉曼分析等证明了 APP/CEPO体系气、固两相的阻燃机理,而APP/HBP体系主要在凝聚相中发挥作用。
[Abstract]:This thesis focuses on the rigid polyurethane foam (RPUF) on combustion toxicity, using classical ammonium polyphosphate / two methyl phosphonic acid methyl ester (APP/DMMP) as the two flame retardant system, with a series of transition metal compounds prepared in the lab, the RPUF composite material of many series were successfully prepared, and its combustion toxicity evaluation system using a variety of techniques, revealing the attenuated mechanism of smoke suppression of various additives. In order to improve the combustion toxicity of flame retardant system of RPUF, based on the original traditional flame retardant system, two kinds of hyperbranched nitrogen phosphorus flame retardant was synthesized, which was introduced into the RPUF system. In addition, in order to explore the possibility of two kinds of hyperbranched flame retardants used in other matrix, it will be introduced to the two poly terephthalate (PBT) and polypropylene (PP). The research work of this thesis is divided into four parts, the paper points as follows : 1) by wet chemical method, with rule eight surface morphology of Cu_2O particles and Cu_2O@CNT hybrids were prepared, Cu_2O@GO. introduced to the flame retardant RPUF system to obtain RPUF composite material. The cone calorimeter test showed that Cu20 and its hybrid makes heat release rate (HRR) and smoke production rate (SPR) decreased significantly. The smoke density test showed that Cu_2O and its hybrids can effectively inhibit the growth of tobacco effect brought by APP/DMMP, and the RPUF composite material is lower than that of the pure smoke samples. The fire toxicity test platform (FTTP) test, 825 C can make Cu_2O play smoke attenuated effect more than 650 degrees Celsius. Thermal infrared analysis showed that the Cu20 material gas escaping strength decreased significantly, and the CO removal rate decreased significantly. Laser Raman analysis showed that Cu_2O and its hybrids to the degree of graphitization of carbon residue materials increased, the change Change of material pyrolysis, carbonization process, the inhibition of.2 for flue gas) through hydrothermal method, a series of carbon encapsulated Fe_20_3@C microspheres were prepared by Cu@C and Cu20@Fe_2O_3@C., the introduction of flame retardant RPUF system, prepared a series of RPUF composite. The cone calorimeter test found that three kinds of microspheres are HRR and SPR decreased significantly, and Fe_20_3@C has the best effect. The smoke density box are presented and the results show that in the tobacco producing three kinds of microspheres are to some extent inhibited the negative effects of APP/DMMP, but failed to reach the level of.FTTP pure RPUF test found at 650 DEG C regardless of ventilation state, each microsphere failed to inhibit RPUF smoke; ventilation condition is not good. The yield of CO decreased. The thermal infrared analysis showed that the microspheres are the material of gas phase evolution intensity decreased, especially in Cu@C is the best. The Raman analyses show that the microspheres are the material The graphitization degree of carbon material increased, especially Fe_2O_3@C was the best, the flue gas barrier suppression of visible microspheres has played a positive role in.3) by solution co precipitation, hydroxy stannate a series of different morphologies were prepared: zinc Hydroxystannate (ZHS), hydroxyl radical (acid copper tin CHS) and hydroxystannates iron (IHS). It will be introduced to the flame retardant RPUF system, a series of RPUF composite materials were prepared. The thermogravimetric analysis showed that the hydroxyl stannate makes the carbon residue of RPUF significantly increased, the degradation temperature intervals and the initial degradation in advance. The test results of cone calorimeter display, ZHS, CHS and IHS HRR inhibition efficiency is low, but it can significantly inhibit SPR. in smoke density test box, three hydroxy stannate also showed.FTTP inhibition efficiency of the smoke test results showed excellent, three kinds of smoke in the inhibition of salt are not ideal, but to make the CO the yield of Ming Dynasty Significantly reduced. Thermal infrared analysis showed that ZHS, CHS and IHS inhibition efficiency of the gas products increased and Raman analysis also found that IHS can improve the degree of graphitization of carbon materials.4) in order to avoid the increasing effect of traditional flame retardant smoke caused by self synthesized hyperbranched nitrogen phosphorus flame retardant and CEPO HBP. applied in RPUF and with various additives, prepared a series of RPUF composite. Test results of cone calorimeter showed 10 HBP instead of 5 APP and 5 HBP, material HRR had significantly decreased, SPR is reduced to a level close to zero. The test results the smoke density display box, smoke production of RPUF/HBP is much lower than that of RPUF/APP/HBP, joined the Cu20, Fe_20_3@C or ZHS after smoke have been further reduced. In FTTP test, RPUF/10HBP smoke is close to pure kind of level, adding 5 phr of ZHS light transmittance is close to 100%.5) for preliminary exploration The CEPO and HBP flame retardant in other polymer matrix in the performance of the APP/CEPO system can be used in PBT, the APP/HBP system can be used in PP, found that two system has a very high flame retardant efficiency, especially when the proportion is 1:1. The best thermal infrared analysis, scanning electron microscopy (SEM) and Raman analysis the proof system of APP/CEPO gas, flame retardant mechanism of solid phase, while the APP/HBP system mainly play a role in condensed phase.

【学位授予单位】：中国科学技术大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ328.3

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