生物基阻燃剂的制备及其阻燃聚丙烯的研究

发布时间：2018-06-13 23:05

本文选题：生物基 + 植酸　；参考：《中北大学》2017年硕士论文

【摘要】：聚丙烯(PP)以其优良的物理、化学性能成为现代生活中用途最广的通用高分子材料。但是PP易燃的特性限制了它在多个领域的应用。近些年,材料的环保与安全成为人们关注的焦点,因此开发环保型阻燃PP一直是研究热点。以生物基原料制备阻燃剂正好满足了安全环保和可持续的趋势,相关研究受到了广泛关注,但是大多数生物基材料耐热性能差,应用领域受到限制,而且大多生物基阻燃剂效率较低,无法作为优异的阻燃剂使用。因此必须通过物理或化学的方法进行合理的处理,赋予其作为阻燃剂的特性,这也是生物基阻燃技术发展的必然措施。本文选用具有阻燃作用的植酸和胞嘧啶(Cy)作为原料,分别制备了植酸金属盐、植酸哌嗪盐(PA-Pi)以及三嗪成炭剂CC-Cy,研究了它们作为阻燃剂组分与商品阻燃剂复合使用在PP中的协同阻燃作用。具体包括以下三部分:1.以具有催化作用的金属离子锌(Zn2+)、镍(Ni2+)、钴(Co2+)为阳离子分别制备了植酸锌(PA-Zn)、植酸镍(PA-Ni)、植酸钴(PA-Co)等植酸金属盐。将其作为协效剂与商品膨胀型阻燃剂(IFR)复合,通过熔融共混法制备了PP复合材料。研究结果表明,PP复合材料中添加2 wt%PA-Zn和17 wt%IFR可以使氧指数达到29.2 vol%,比单独添加19 wt%IFR的氧指数提高5.1 vol%。同样添加1 wt%的PA-Ni与17 wt%IFR可以使PP复合材料氧指数达29.5 vol%,同样含量的PA-Co则使PP复合材料氧指数达28.6 vol%,并且两者均通过了UL-94 V-0级别的测试。这些结果表明,PA-Ni与PA-Co的对阻燃效率的提升作用略优于PA-Zn。通过热失重分析(TGA)、扫描电镜(SEM)、拉曼(Raman)光谱等分析了阻燃机理,结果发现植酸金属盐有助于提高IFR在高温下的交联度及稳定性,提高成炭率。而且植酸金属盐的加入改善了炭层质量,使残炭膨胀并产生很多褶皱,更好地阻隔气体和热量的交换,但是炭层中并未观察到新结构的形成,故这些植酸金属盐应该主要改变了成炭速度和质量,因而提高了阻燃效率。2.以哌嗪作为阳离子与植酸反应制备了PA-Pi,将其作为酸源与炭源双季戊四醇(DPER)复配,通过熔融共混法制备了阻燃PP复合材料。改变阻燃剂体系的复合比例和添加量,发现总添加量为25 wt%,PA-Pi:DPER为3:1时,PP复合材料的氧指数为28.1 vol%,达到了UL-94 V-0级别。通过TGA、SEM、Raman光谱等分析了阻燃机理,TGA研究发现PA-Pi与DPER之间的化学反应比较复杂,前期催化提前降解,后期则促进交联成炭。SEM及Raman光谱分析表明,随着阻燃剂添加量的增加,炭层更完整致密,缺陷明显减少并且规整度提高,炭层质量变好,因而获得了更高的阻燃效率。3.采用胞嘧啶与三聚氯氰反应制备了三嗪成炭剂CC-Cy,将其与聚磷酸铵(APP)和双酚A双(二苯基磷酸酯)(BDP)组成IFR体系,并用来提高PP的阻燃性能。结果显示PP中含20 wt%APP与5 wt%CC-Cy可以达到UL-94 V-2级别。而含18 wt%的APP/CC-Cy复合物APP:CC-Cy=4:1)与3 wt%BDP时,PP复合材料就可以达到UL-94 V-0级别,这说明三者间存在明显的协同作用,使阻燃效率得到提高。阻燃机理分析表明,APP与CC-Cy的反应促进了残炭的生成,BDP的加入进一步提高了成炭性能。红外热成像发现BDP可以降低样品点燃后表面的温度,而且还发现BDP不仅在气相中发挥作用,同时促进了固相中的成炭反应。APP、CC-Cy、BDP三者之间的良好协同,促进了有效的保护炭层的形成,提高了阻燃效率。
[Abstract]:Polypropylene (PP) has become the most widely used general polymer material in modern life for its excellent physical and chemical properties. However, the flammability of PP restricts its application in many fields. In recent years, the environmental protection and safety of materials have become the focus of attention. Therefore, the development of environment-friendly flame retardant PP has always been a hot topic. As the flame retardants meet the safety and sustainability trend, the related research has received extensive attention, but most biologically based materials are poor in heat resistance and limited in application fields, and most of the bio-based flame retardants are inefficient and can not be used as excellent flame retardants. Therefore, physical or chemical methods must be used in combination. In this paper, phytic acid and cytosine (Cy) with flame retardancy were used as raw materials to prepare phytic acid metal salts, phytic piperazine salts (PA-Pi) and three azine carbonizing agents, CC-Cy, which were used as flame retardants and flame retardants. The synergistic flame retardancy used in PP is composed of three parts: 1. the zinc phytate (PA-Zn), nickel phytate (PA-Ni), cobalt phytate (PA-Co) and other phytate metal salts are prepared respectively with metal ion zinc (Zn2+) with catalytic action, nickel (Ni2+) and cobalt (Co2+) as cations, respectively, as synergist and commodity expansive flame retardant (IFR). PP composites were prepared by over melt blending. The results showed that the oxygen index reached 29.2 vol% by adding 2 wt%PA-Zn and 17 wt%IFR in the PP composite, and the oxygen index of 19 wt%IFR was increased by 5.1 vol%., and the PA-Ni and 17 wt%IFR of 1 wt% could make the oxygen index of PP composite up to 29.5 vol%. The oxygen index of PP composites reached 28.6 vol% and both passed the test of UL-94 V-0 level. These results showed that the effect of PA-Ni and PA-Co on the improvement of flame retardancy was slightly better than that of PA-Zn. through thermal weight loss analysis (TGA), scanning electron microscopy (SEM), and Raman (Raman) spectroscopy. The results showed that phytate metal salts help to increase IFR. The crosslinking degree and stability at high temperature increase the carbon formation rate. Moreover, the addition of phytic acid improves the quality of the carbon layer, causes the carbon residue to expand and produces many folds, and better obstruct the exchange of gas and heat. However, the formation of the new structure is not observed in the carbon layer, so these phytate metal salts should mainly change the speed and quality of carbon formation. Therefore, the flame retardancy efficiency of.2. was improved by the reaction of piperazine as a cation and phytic acid to prepare PA-Pi, which was used as an acid source and carbon source bis pentaerythritol (DPER), and the flame retardant PP composite was prepared by melt blending. The composite ratio and addition amount of the flame retardant system were changed, and the total addition amount was 25 wt% and PA-Pi:DPER was 3:1, PP composite material was found. The oxygen index of the material was 28.1 vol% and reached the level of UL-94 V-0. The flame retardant mechanism was analyzed by TGA, SEM and Raman spectra. The TGA study found that the chemical reaction between PA-Pi and DPER was more complex, early catalytic degradation, and later promoted cross-linking to carbon.SEM and Raman spectral analysis, and the carbon layer was more complete with the increase of the addition of flame retardant. The defects are obviously reduced and the regularity is improved and the quality of the carbon layer is better. Therefore, a higher flame retardant efficiency.3. is obtained by the reaction of cytosine and cyanuric chloride to prepare the three azimuth carbon forming agent CC-Cy, which is formed with ammonium polyphosphate (APP) and bisphenol A double (two phenyl phosphate) (BDP) as IFR system, and is used to improve the flame retardancy of PP. The results show PP in PP. 20 wt%APP and 5 wt%CC-Cy can reach the level of UL-94 V-2. With the APP/CC-Cy complex of 18 wt%, APP:CC-Cy=4:1) and 3 wt%BDP, the PP composite can reach UL-94 V-0. This shows that there is a significant synergism between the three and the flame retardancy efficiency is improved. The addition of BDP further improves the charcoal performance. Infrared thermal imaging shows that BDP can reduce the temperature of the surface after the sample is ignited. Moreover, it is found that BDP not only plays a role in the gas phase, but also promotes the good CO formation of the carbon forming reaction of the solid phase,.APP, CC-Cy, BDP three, which promotes the formation of the carbon layer effectively and improves the resistance of the carbon layer. Combustion efficiency.
【学位授予单位】：中北大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ325.14

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