【作者】 徐元清；

【导师】 王彦林；

【作者基本信息】 河南大学 ， 高分子化学与物理， 2003， 硕士

【摘要】 阻燃剂是用以提高材料抗燃性，即阻止材料被引燃及抑制火焰传播的助剂。溴系阻燃剂和磷系阻燃剂是有机阻燃剂的主要品种。本文主要合成了两种溴系阻燃剂：高效低毒阻燃剂十溴二苯乙烷和2,3-二溴丁二酸酐，两种磷系阻燃剂：阻燃增塑剂IPP和膨胀型阻燃剂BPMPA，并对它们的应用进行了初步探讨。合成的第一个溴系阻燃剂为新型高效低毒阻燃剂十溴二苯乙烷。十溴二苯醚是用量最大的溴系阻燃剂，但“dioxin"问题使得其应用倍受非议。十溴二苯乙烷具有阻燃效率高、原料价廉易得、燃烧时不产生“dioxin"等优点，是十溴二苯醚的理想取代品，可广泛应用于聚烯烃、工程塑料、电线电缆及橡胶中。首先对其关键性中间体1,2-二苯乙烷的合成进行了研究。从易于工业化的角度，选择了两种方法合成1,2-二苯乙烷：1、烷基化方法以苯和二氯乙烷为原料，对该合成的工艺条件进行了优化选择，并对苯和催化剂的回收利用问题进行了讨论。2、偶联法以苄基氯和铁为原料，采用正交实验的方法对工艺条件进行了优化并比较了各种影响因素的影响大小；对后处理进行了改进，采用加酸溶解铁粉后趁热分液、甲醇重结晶的方法，具有产品收率高、设备投资小、操作简单、步骤少、能耗低、产品质量较高等优点。3、对两种合成方法的比较表明：烷基化方法原料成本低，但偶联法在环保、操作及设备投资等方面具有优势。对十溴二苯乙烷的合成工艺条件进行了优化选择，并首先解决了二苯乙烷的液态连续滴加问题，最后采用微碱性条件下研磨、高温下烘焙的方法提高产品质量，产品质量接近美国同种产品水平。合成的第二个溴系阻燃剂是新型反应型阻燃剂2,3-二溴丁二酸酐。与添加型阻燃剂相比，反应型阻燃剂不仅可使材料达到永久性阻燃，而且基本不影响其优异性能。在酸（酐）类反应型阻燃剂中四溴苯酐的用量最大，但其价格昂贵；2,3-二溴丁二酸酐的含溴量高、阻燃性能好、原料价廉易得，目前文献鲜有报道，更无商品出售。对2,3-二溴丁二酸酐的合成采用直接溴化加成的方法，与取代法相比，溴素利用率高、设备腐蚀小；选择了无毒无污染的溶剂，无需催化剂；粗产品的<WP=3>提纯采用蒸馏重结晶的方法，可得到纯度较高的产品。以上合成及提纯方法未见报道。合成的第一个磷系阻燃剂为阻燃增塑剂IPP(异丙苯基苯基磷酸酯)。阻燃增塑剂因具有阻燃和增塑的双重功能而受到青睐，磷酸三甲苯酯(TCP)曾是用量最大的一种，但其毒性大、生产成本高。IPP性能优异，且生产成本低，又无毒无味，可应用于聚烯烃、橡胶、塑料运输带、电线电缆、人造革等。该反应分两部分：烷基化反应中采用对羟基苯磺酸为催化剂，并对工艺条件进行了优化；酯化反应的后处理过程中，采用加入定量水后过滤的方法除去AlCl3,与酸洗法相比，具有工艺简单、污染少、产品质量高等特点；产品质量经检验完全符合中华人民共和国HG/T 2425-93优等品的标准。该烷基化催化剂及酯化后处理方法未见文献报道。合成的第二个磷系阻燃剂为膨胀型阻燃剂环状磷酸酯N,N’-双（2-氧代-5,5-二甲基-1,3,2-二氧磷杂环己基-2）间苯二胺（BPMPA）。 膨胀型阻燃剂被认为是未来阻燃剂的发展方向之一，它无需协效剂，可单独使用；燃烧时不会产生大量的烟尘及有毒气体，符合绿色环保的要求；不产生融滴，这一点对于聚烯烃的阻燃尤为重要。对合成BPMPA的工艺进行了探讨，并经红外和元素分析对产品结构进行了鉴定。对上述合成的阻燃剂的应用进行了初步探讨。对它们的热分析表明，十溴二苯乙烷、阻燃增塑剂IPP及BPMPA均具有很好的热稳定性，其热分解温度与多数聚合物的热氧降解温区重叠，具有较好的阻燃配伍性能。将它们用于软PVC、不饱和聚酯树脂等中的阻燃，实验结果表明：十溴二苯乙烷在软PVC中具有优异的阻燃效能，其最佳锑溴比为1/3，最佳溴含量为13.7%；在PS中也具有较好的阻燃性能，其最佳锑溴比为1/6；在不饱和聚酯树脂中，有一定的阻燃作用，当三锑溴比为1/6时，有最佳的阻燃效果。阻燃增塑剂IPP在软PVC中，既具有较好的阻燃性，同时还对材料有良好的增塑性，具有阻燃和增塑的双重功能。膨胀型阻燃剂BPMPA具有较高的成炭率，对软PVC也具有良好的阻燃作用。更多还原

【Abstract】 Flame retardant (FR) is a kind of additive which can enhance the material’s flame resistance. Among the organic flame retardants, brominated and phosphorus- containing flame retardants are the most important. Although "dioxin" problem of polybromodiphenyl ethers made it be challenged, brominated flame retardant will keep its leading position in FRs. In this dissertation, two brominated FRs and two phosphorous-containing FRs were prepared and their preliminary applications in polymers were also discussed.The first brominated FR was a novel, high efficient and low toxic flame retardant decabromo-diphenyl ethane (DBDPE), the ideal substitution of decabromo-diphenyl ether. DBDPE has a high bromine content, with low toxicity when burns. It can be used widely in polyolefin, engineering plastics, electric wire and cable, rubber and so on. First of all, the key intermediate product of DBDPE-- diphenylethane (DPE) was studied. In an easy-to-industrialized way, two methods were choosed. First was alkylation reaction, this method used benzene and dichloroethane as raw materials. The optimum processing conditions were determined, furthermore, the recycle of benzene and catalyze were also discussed. Second was coupling reaction, using benzyl chloride and powdered iron as raw materials. After an orthogonal experiment, the process optimization was established. In addition, the effects of the influencing factors were compared. During the post-treatment, the redundant iron was resolved by acid, then after separation, the product was directly recrystallized. This process has many advantages such as high productivity, low equipment investment, simple operation and low energy consumption etc. The comparison between these methods indicated that: the former alkylation’s has superiorities in feed stock cost, but the latter has vantages in environmental protection, operation and equipment investment. <WP=5>Subsequently, the FR DBDPE was synthesized. The process was optimized. Firstly solved problem was how to dropwise continuously in liquid state. Secondly was to upraise the quality of products. After a long-term grind and baking under high temperature, the product reached high quality.The second synthesized brominated FR was a new reactive-type flame retardant 2,3-Dibromosuccinic Anhydride. Contrast to the additive FR, reactive FRs seldom interfere with the material’s excellent performance, and bestow the material permanent flame retardancy at the same time. By a direct addition reaction, bromine was utilized utterly, without corrosion to the equipments. The solvent selected has no toxicity, no pollution and easy to recycled, while the reaction needs no catalyst. To purify the rough product, a new method was established, we called it distillatory recrystallization.The first phosphorus-containing FR synthesized was flame retarding plasticizer isopropylphenyldiphenyl phosphate ester (IPP). Flame retarding plasticizer has double functions: good flame retardancy and plasticity as well, as is appreciated by many consumers. The most popular flame retarding plasticizer was trimethylphenyl phosphate ester (TCP) once, but it is toxic and costs high. IPP has low toxicity and cost, with outstanding performance as TCP, which makes it the substitution of TCP. IPP was synthesized from POCl3, phenol and propene etc. The alkylation catalyst phenol sulfonic acid was selected. Meanwhile, the optimum alkylation and esterification reaction conditions were determined. During the after-treatment process, the esterification catalyst AlCl3 was removed with a physical and chemical combined process. This process has advantages as simple operation, low pollution and high quality of products. Eventually, the quality inspection manifested that the product coincided the classy of the national standard. The last FR was an intumescent flame retardant (IFR), N, N’-di (2-oxo-5, 5-dimethyl -1, 3, 2-dioxy-phosphacyclohexane)-2, 2’-m-phenylene diamine (BPMPA).<WP=6>IFR was considered the develop direction of the FRs. It can be used alone, nee更多还原