无卤阻燃剂的合成及其阻燃聚碳酸酯的研究
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摘要
聚碳酸酯(PC)是一种具有高抗冲击强度、透明性、耐热性、尺寸稳定性和优异的电绝缘性工程塑料。PC的热分解温度高,自身具有一定的阻燃性,大多数的PC的氧指数为21%~24%范围内,阻燃等级达UL 94 V-2级。虽然本身能自熄,但当它应用于电子电器行业时,必须进行阻燃改性。
随着人们环保意识的增强和国际上禁止使用卤素的呼声越来越高,开发新型无卤阻燃剂已成为当前阻燃剂发展的热点,磷系阻燃剂正受到人们的关注,并且已经开发出了一系列以有机磷为主要成分的新型无卤阻燃剂。
本文采用Friedel-Crafts反应,以三氯化磷和苯为原料,制备中间产物苯基硫代膦酰二氯(DCPPS),再与甲苯反应,制备得到双(对-甲苯基)苯基硫化膦(BMPPS)。通过考察反应物的配比,催化剂的加入量和反应时间对DCPPS和BMPPS产率的影响,探索出较佳的合成工艺条件。还考察了BMPPS添加量对PC/BMPPS复合材料力学性能、热性能和燃烧性能的影响。结果表明:当阻燃剂用量为4%,PC/BMPPS材料达UL94 V-0级(3.2mm),氧指数(OI)达30.6%。BMPPS加入虽不能增加PC的成炭率,却可加速PC材料的交联成炭。
有机硅作为阻燃剂的成分逐渐引起人们的注意,研究表明硅化合物能和磷起到协同阻燃的作用。本文合成了两种含磷、氮、硅于同一分子的阻燃剂PNSi,通过红外光谱、核磁共振氢谱以及磷谱对产物的结构进行分析表征;通过热重分析对其热性能进行研究,其700℃时的成炭率超过30%。
最后,本文研究了PNSi对PC阻燃性能及热性能的影响,结果表明:PNSi的加入能提高PC的氧指数及成炭率。动力学分析表明,阻燃剂的加入使得活化能先降低后提高。样品残炭的红外光谱研究表明了PNSi在成炭过程中起了重要的作用,PNSi能通过磷酸酯和硅氧烷的一系列反应,使得含硅的物质在PC的炭层表面堆积,从而提高材料的高温热稳定性。
Polycarbonate (PC) is commonly used as a high-performance amorphous engineering thermoplastic dues to its outstanding properties, including high impact strength, transparency, heat resistance, dimensional stability, and excellent electrical properties. For the flame retardant properties of PC, it shows a V-2 rating in the UL-94 test and it’s oxygen index is between 21% to 24%. But strict flame retardant performance is often required for electronic and electric applications, the flame retardant technologies of polycarbonate have been developed.
As people are paying more attention to the environment and the requirement of forbidding using halogen grows, development of novel non-halogen FR becomes a focus nowadays, and phosphorus is attracting a lot of attention. Certain numbers of new non-halogen FR have been developed based on phosphorus.
In this paper, phenyl phosphonothioic dichloride (DCPPS) was synthesized from phosphorus trichloride and benzene through the Friedel-Crafts reaction, toluene was then used to react with DCPPS to get the desired product—bis(4-methylphenyl)phenyl phosphine sulfide(BMPPS). The effects of feed composition, catalyst concentration and reflux reaction time on DCPPS and BMPPS yield were investigated. The effect of BMPPS on the mechanical properties, thermal properties and flame retardancy of PC was also investigated. The results show that: with the addition of 4% BMPPS, PC/BMPPS is up to UL94 V-0 (3.2mm), the OI of PC is up to 30.6%. Thermal decomposition datum show that BMPPS can't improve the char yield of PC, but it can accelerate crosslinking and char forming of PC.
Silicone starts attracting people's attention as an effect part of FR. It's reported that there are some synergetic function between silicon and phosphorus. In this paper, two novel flame retardants containing phosphorus, nitrogen and silicon were synthesized. The chemical structure of the intermediates and flame retardants were investigated by infrared spectroscopy (IR) and nuclear magnetic resonance (NMR).The thermal stability of the flame retardants were investigated by TGA under air and nitrogen, and char yield more than 30% can be got at 700℃
Last, the effect of PNSi on the flame retardancy and thermal properties of PC were investigated.The PNSi enhance the flame retardancy of PC successfully through the results of LOI test .TGA result reveals the addition of PNSi improves the high thermal stability of PC. IR analysis confirmed that the P and Si played a great role in process of char forming. PNSi changed the degradation molding of PC by a series reaction of phosphate ester and siloxane and formed the char abundant in Si.The char acted as a good barrier to the transfer of heat and combustible gas between the flame zone and the substrate, and thus protected the underlying materials from further burning.
随着人们环保意识的增强和国际上禁止使用卤素的呼声越来越高,开发新型无卤阻燃剂已成为当前阻燃剂发展的热点,磷系阻燃剂正受到人们的关注,并且已经开发出了一系列以有机磷为主要成分的新型无卤阻燃剂。
本文采用Friedel-Crafts反应,以三氯化磷和苯为原料,制备中间产物苯基硫代膦酰二氯(DCPPS),再与甲苯反应,制备得到双(对-甲苯基)苯基硫化膦(BMPPS)。通过考察反应物的配比,催化剂的加入量和反应时间对DCPPS和BMPPS产率的影响,探索出较佳的合成工艺条件。还考察了BMPPS添加量对PC/BMPPS复合材料力学性能、热性能和燃烧性能的影响。结果表明:当阻燃剂用量为4%,PC/BMPPS材料达UL94 V-0级(3.2mm),氧指数(OI)达30.6%。BMPPS加入虽不能增加PC的成炭率,却可加速PC材料的交联成炭。
有机硅作为阻燃剂的成分逐渐引起人们的注意,研究表明硅化合物能和磷起到协同阻燃的作用。本文合成了两种含磷、氮、硅于同一分子的阻燃剂PNSi,通过红外光谱、核磁共振氢谱以及磷谱对产物的结构进行分析表征;通过热重分析对其热性能进行研究,其700℃时的成炭率超过30%。
最后,本文研究了PNSi对PC阻燃性能及热性能的影响,结果表明:PNSi的加入能提高PC的氧指数及成炭率。动力学分析表明,阻燃剂的加入使得活化能先降低后提高。样品残炭的红外光谱研究表明了PNSi在成炭过程中起了重要的作用,PNSi能通过磷酸酯和硅氧烷的一系列反应,使得含硅的物质在PC的炭层表面堆积,从而提高材料的高温热稳定性。
Polycarbonate (PC) is commonly used as a high-performance amorphous engineering thermoplastic dues to its outstanding properties, including high impact strength, transparency, heat resistance, dimensional stability, and excellent electrical properties. For the flame retardant properties of PC, it shows a V-2 rating in the UL-94 test and it’s oxygen index is between 21% to 24%. But strict flame retardant performance is often required for electronic and electric applications, the flame retardant technologies of polycarbonate have been developed.
As people are paying more attention to the environment and the requirement of forbidding using halogen grows, development of novel non-halogen FR becomes a focus nowadays, and phosphorus is attracting a lot of attention. Certain numbers of new non-halogen FR have been developed based on phosphorus.
In this paper, phenyl phosphonothioic dichloride (DCPPS) was synthesized from phosphorus trichloride and benzene through the Friedel-Crafts reaction, toluene was then used to react with DCPPS to get the desired product—bis(4-methylphenyl)phenyl phosphine sulfide(BMPPS). The effects of feed composition, catalyst concentration and reflux reaction time on DCPPS and BMPPS yield were investigated. The effect of BMPPS on the mechanical properties, thermal properties and flame retardancy of PC was also investigated. The results show that: with the addition of 4% BMPPS, PC/BMPPS is up to UL94 V-0 (3.2mm), the OI of PC is up to 30.6%. Thermal decomposition datum show that BMPPS can't improve the char yield of PC, but it can accelerate crosslinking and char forming of PC.
Silicone starts attracting people's attention as an effect part of FR. It's reported that there are some synergetic function between silicon and phosphorus. In this paper, two novel flame retardants containing phosphorus, nitrogen and silicon were synthesized. The chemical structure of the intermediates and flame retardants were investigated by infrared spectroscopy (IR) and nuclear magnetic resonance (NMR).The thermal stability of the flame retardants were investigated by TGA under air and nitrogen, and char yield more than 30% can be got at 700℃
Last, the effect of PNSi on the flame retardancy and thermal properties of PC were investigated.The PNSi enhance the flame retardancy of PC successfully through the results of LOI test .TGA result reveals the addition of PNSi improves the high thermal stability of PC. IR analysis confirmed that the P and Si played a great role in process of char forming. PNSi changed the degradation molding of PC by a series reaction of phosphate ester and siloxane and formed the char abundant in Si.The char acted as a good barrier to the transfer of heat and combustible gas between the flame zone and the substrate, and thus protected the underlying materials from further burning.
引文
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