磷系阻燃剂BDP的合成及无卤阻燃PPO/HIPS合金的研究
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摘要
聚苯醚(PPO)是美国通用电气公司(GE)于20世纪60年代中期开发的热塑性树脂,属于五大通用工程塑料之一。作为具有优良的物理力学性能、耐热性和电气绝缘性的聚苯醚,存在着黏度高、流动性差、对缺口较敏感等缺陷,一般需要对其进行改性。通常对聚苯醚的改性是将聚苯醚和聚苯乙烯尤其是高抗冲聚苯乙烯共混。聚苯醚的阻燃性能良好,具有自熄性,但是高抗冲聚苯乙烯属于易燃材料,二者合一则使得材料的阻燃性能明显降低,故必须加入适当的阻燃剂使其阻燃性能达到使用要求。目前常用的阻燃剂主要有卤系和磷系阻燃剂。卤系阻燃剂在燃烧过程中生成很多烟雾和腐蚀性气体,甚至产生剧毒物质二嗯英,欧盟有些国家已经颁布法令禁止使用此类阻燃剂。
磷酸酯用作聚合物的阻燃剂已有多年历史,随着阻燃剂研究的不断向前发展,磷酸酯类阻燃剂已经逐渐从单磷酸酯向多聚磷酸酯类过渡。尤其是双磷酸酯的齐聚物,具有结构对称、相对分子质量高、磷含量高等特点,其增塑性、阻燃性、热稳定性均优于普通磷酸酯。这类阻燃剂与聚合物的相容性好,因此得到了广泛的应用。双酚A双(二苯基磷酸酯)(BDP)属于双磷酸酯齐聚物阻燃剂中的杰出代表,国外已有该产品的生产,而国内尚处于研发阶段,暂时没有工业化产品。
本文首先合成无卤环保高效的磷系阻燃剂双酚A双(二苯基磷酸酯)(BDP)。找到了最适宜的合成路线和反应条件,并改进了后处理方式和工艺以提高能源利用率和原料利用率从而为规模化的工业生产做准备。之后将BDP添加到PPO/HIPS合金中去提高材料的阻燃性能,结果表明BDP对合金的阻燃效率良好,对材料的力学性能损失较小且能提高合金的加工性能；随后采用氮系和无机系的等价格较为便宜的无卤阻燃剂对PPO/HIPS合金进行阻燃研究,发现这两种无卤阻燃剂对材料的阻燃效率一般且对材料的冲击性能影响较大,对材料的加工性能的负面影响不可忽略。为了提高前述两种阻燃方式的阻燃效率,最后采用复配阻燃的方式,将氮系和无机系的阻燃剂同磷系阻燃剂进行复配使用,实验结果表明采用复配阻燃的方式可以使阻燃效率大为提高,而且相比单纯用磷系阻燃剂阻燃材料还具有成本上的优势。更为重要的是采用和磷系阻燃剂复配的方式可以降低氮系和无机系阻燃剂对材料的力学性能和加工性能的损失。综合考虑最优的阻燃方式为改性高岭土复配BDP。
As one of the five largest general engineering plastics, Thermoplastic resin Polyphenylene oxide (PPO) was developed by the General Electric Company (GE) in the mid 60s,20th century. Although PPO has excellent physical and mechanical properties, heat resistance and electrical insulation, it has defects such as high viscosity, poor mobility, very sensitive to notch. So it needs modification. Usually the modification is blend polyphenylene oxide with polystyrene, especially high impact polystyrene. Polyphenylene oxide has a good flame retardant property and its an extinguishing resin. But high impact polystyrene is a flammable materials, the alloy of the two has a weak flame retardant property. Because of these reasons, we need to add some suitable flame retardants on the ally to improve its flame retardant property. Commonly, the most used flame retardants are halogenated and phosphorus flame retardants. Halogenated flame retardants generate a lot of smoke and corrosive gases or even highly toxic dioxins during the combustion process. Some countries in the European Union have enacted laws to prohibit the use of such flame retardants.
Phosphate ester flame retardants has been used in polymers for many years. With the development of the flame retardants research, phosphate ester flame retardants have been changed from single phosphate ester to polyphosphate. Especially the oligomer of double phosphate. They have advantages of symmetrical structure, high molecular weight and high phosphorus content. They are good plasticizers which are better than normal phosphates in flame resistance and thermal stability. They have good compatibility with polymers and had been widely applied. Bisphenol A bis (diphenyl phosphate) (BDP) is an outstanding representative in such flame retardants. There has industrial products abroad, while in China its still under development and has no industrial products.
In this paper, environmental protection and high efficient Halogen-free flame retardant bisphenol A bis (diphenyl phosphate) (BDP) was synthesized first. We found the most appropriate synthetic route and reaction conditions for BDP, and improved post-processing methods and techniques to increase raw materials and energy's utilization rate so as for the preparation of large-scale industrial production of BDP. Then we added BDP to the PPO/HIPS alloy to improve its flame retardant property, the results show that the BDP has good flame retardant property to the alloy, it has a small mechanical property loss to the material and can improve the processability of the alloy; After that we used another two less expensive halogen-free flame retardants which are nitrogen containing and inorganic flame retardants on PPO/HIPS alloy and found that the effects of the other two flame retardants are just so so. They have a big impact on alloy's impact strength and its processability. In order to improve the flame retardant efficiency, compounding method was used finally. The other two flame retardants were compounded with phosphorus flame retardant. It was founded that the compounding method can improve flame retardant efficiency and cost less than phosphorus flame retardant. What's more, compounding method can reduce mechanical property and processability loss of PPO/HIPS alloy. Comparison shows that the best way is using modified kaolin compounded with BDP.
磷酸酯用作聚合物的阻燃剂已有多年历史,随着阻燃剂研究的不断向前发展,磷酸酯类阻燃剂已经逐渐从单磷酸酯向多聚磷酸酯类过渡。尤其是双磷酸酯的齐聚物,具有结构对称、相对分子质量高、磷含量高等特点,其增塑性、阻燃性、热稳定性均优于普通磷酸酯。这类阻燃剂与聚合物的相容性好,因此得到了广泛的应用。双酚A双(二苯基磷酸酯)(BDP)属于双磷酸酯齐聚物阻燃剂中的杰出代表,国外已有该产品的生产,而国内尚处于研发阶段,暂时没有工业化产品。
本文首先合成无卤环保高效的磷系阻燃剂双酚A双(二苯基磷酸酯)(BDP)。找到了最适宜的合成路线和反应条件,并改进了后处理方式和工艺以提高能源利用率和原料利用率从而为规模化的工业生产做准备。之后将BDP添加到PPO/HIPS合金中去提高材料的阻燃性能,结果表明BDP对合金的阻燃效率良好,对材料的力学性能损失较小且能提高合金的加工性能；随后采用氮系和无机系的等价格较为便宜的无卤阻燃剂对PPO/HIPS合金进行阻燃研究,发现这两种无卤阻燃剂对材料的阻燃效率一般且对材料的冲击性能影响较大,对材料的加工性能的负面影响不可忽略。为了提高前述两种阻燃方式的阻燃效率,最后采用复配阻燃的方式,将氮系和无机系的阻燃剂同磷系阻燃剂进行复配使用,实验结果表明采用复配阻燃的方式可以使阻燃效率大为提高,而且相比单纯用磷系阻燃剂阻燃材料还具有成本上的优势。更为重要的是采用和磷系阻燃剂复配的方式可以降低氮系和无机系阻燃剂对材料的力学性能和加工性能的损失。综合考虑最优的阻燃方式为改性高岭土复配BDP。
As one of the five largest general engineering plastics, Thermoplastic resin Polyphenylene oxide (PPO) was developed by the General Electric Company (GE) in the mid 60s,20th century. Although PPO has excellent physical and mechanical properties, heat resistance and electrical insulation, it has defects such as high viscosity, poor mobility, very sensitive to notch. So it needs modification. Usually the modification is blend polyphenylene oxide with polystyrene, especially high impact polystyrene. Polyphenylene oxide has a good flame retardant property and its an extinguishing resin. But high impact polystyrene is a flammable materials, the alloy of the two has a weak flame retardant property. Because of these reasons, we need to add some suitable flame retardants on the ally to improve its flame retardant property. Commonly, the most used flame retardants are halogenated and phosphorus flame retardants. Halogenated flame retardants generate a lot of smoke and corrosive gases or even highly toxic dioxins during the combustion process. Some countries in the European Union have enacted laws to prohibit the use of such flame retardants.
Phosphate ester flame retardants has been used in polymers for many years. With the development of the flame retardants research, phosphate ester flame retardants have been changed from single phosphate ester to polyphosphate. Especially the oligomer of double phosphate. They have advantages of symmetrical structure, high molecular weight and high phosphorus content. They are good plasticizers which are better than normal phosphates in flame resistance and thermal stability. They have good compatibility with polymers and had been widely applied. Bisphenol A bis (diphenyl phosphate) (BDP) is an outstanding representative in such flame retardants. There has industrial products abroad, while in China its still under development and has no industrial products.
In this paper, environmental protection and high efficient Halogen-free flame retardant bisphenol A bis (diphenyl phosphate) (BDP) was synthesized first. We found the most appropriate synthetic route and reaction conditions for BDP, and improved post-processing methods and techniques to increase raw materials and energy's utilization rate so as for the preparation of large-scale industrial production of BDP. Then we added BDP to the PPO/HIPS alloy to improve its flame retardant property, the results show that the BDP has good flame retardant property to the alloy, it has a small mechanical property loss to the material and can improve the processability of the alloy; After that we used another two less expensive halogen-free flame retardants which are nitrogen containing and inorganic flame retardants on PPO/HIPS alloy and found that the effects of the other two flame retardants are just so so. They have a big impact on alloy's impact strength and its processability. In order to improve the flame retardant efficiency, compounding method was used finally. The other two flame retardants were compounded with phosphorus flame retardant. It was founded that the compounding method can improve flame retardant efficiency and cost less than phosphorus flame retardant. What's more, compounding method can reduce mechanical property and processability loss of PPO/HIPS alloy. Comparison shows that the best way is using modified kaolin compounded with BDP.
引文
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