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阻燃PET/PC共混物的制备、性能及阻燃机理
论文作者:童鞋论文网  论文来源:www.txlunwenw.com  发布时间:2019/9/6 7:47:37  

摘要:聚(对苯二甲酸乙二醇酯) (PET)由于其透明性、高耐化学性和尺寸稳定性等优点,在现代社会受到了广泛的应用,是最重要且用量最多的聚合物材料之一。但纯PET树脂易燃并产生严重的熔滴。PET作为工程塑料使用的许多场合,对其阻燃性与抗熔滴性的要求十分严格,需要提高其阻燃级别。本论文以聚碳酸酯(PC)为成炭剂、溴化聚苯乙烯(或氨基硅油)为阻燃剂,采用熔融共混的方法,在双螺杆挤出机上制备了PET/PC/阻燃剂共混物。通过万能试验机、垂直燃烧测试(UL-94)、极限氧指数测试(LOI)、热重分析(TGA)、热重-红外联用(TG-IR)、锥形量热测试、炭层元素分析(EDS)、炭层红外、扫描电子显微镜(SEM)等研究了共混材料的力学性能、阻燃性能、热稳定性、燃烧行为和阻燃机理。主要研究内容和结果如下:

(1) 研究了环保型含溴高分子阻燃剂溴化聚苯乙烯(BPS)和PC用量对共混物的阻燃、力学性能和燃烧行为的影响。结果表明当PET/PC/BPS的配方比为50/50/10时,共混物的氧指数达到了27%,并可通过UL94 V-0等级测试。BPS的加入与PC含量的增加降低了阻燃材料的热释放与烟释放,表现出更好的阻燃性能。力学测试结果表明BPS的加入降低了共混物的力学性能,而PC含量的添加则提高了共混材料的力学性能。

(2) 研究了PET/PC/BPS共混物的阻燃机理。TGA与SEM测试表明BPS的加入,可以促进燃烧时基体提前成炭,燃烧后生成的炭层完整、蜂窝状孔洞明显且分布均匀规则。TG-IR测试表明阻燃作用主要发生在PET分解的第一阶段;BPS添加量的增加可以有效促进PC分解生成大量CO2,表现出较好的气相阻燃机理。

(3) 研究了氨基硅油(ASO)对PET/PC/ASO共混物的阻燃性能和燃烧行为的影响。阻燃测试结果表明,当添加0.5phr的ASO时,共混物可通过UL 94 V-0等级燃烧试验测试;锥形量热分析结果表明,ASO的添加量越高,PHRR的峰值出现时间推迟并变低,持续放热过程变宽。

(4) 探究了PET/PC/ASO共混物的阻燃机理。热重分析结果表明ASO的添加会推迟基体在初期的分解,一定程度上促进了分解速率的提升并提升了炭层强度。TG-IR测试表明ASO的加入使共混物具有一定的气相阻燃作用。对残炭进行红外、SEM与EDS测试表明伴随着阻燃剂含量的增加,基体的燃烧分解更加完全,CO2生成的更多,起到气相阻燃作用;同时在基体表面生成更多的Si-C键架构起的高强度碳硅骨架,起到凝聚相阻燃的作用。

Poly(ethylene terephthalate) (PET) is widely used in modern society due to its transparency, high chemical resistance and dimensional stability. It is one of the most important and most used polymer materials. However, pure PET resin is flammable and produces serious droplets. There are some harsh requirements on the flame retardancy and antidripping of  PET in many occasions where PET is used as an engineering plastic, it is thus necessary to increase its flame retardant level. In this essay, using polycarbonate (PC) as a carbon-forming agent and brominated polystyrene (or amino silicone oil) as a flame retardant, PET/PC/flame retardant blends were prepared on a twin-screw extruder by melt blending. The mechanical properties, flame retardancy, thermal stability, combustion behavior and flame retardant mechanism of the blended materials were investigated via universal testing machine, vertical burning test (UL-94), limiting oxygen index test (LOI), thermogravimetric analysis (TGA), thermogravimetry-infrared (TG-IR), cone calorimetry, carbon layer elements Analysis (EDS), carbon layer infrared, scanning electron microscopy (SEM), respectively. The main research and results are as follows:

(1) The effects of brominated polystyrene (BPS) and PC on the flame retardancy, mechanical properties and combustion behaviors of the blends were investigated. The results showed that the oxygen index reached 27% and the blends passed UL 94 V-0 testing in the case of 50/50/10 of PET/PC/BPS. The data obtained from cone calorimetry revealed that the addition of BPS and the increasing PC content reduced the heat release and smoke release of the blends, showing a better flame retardant properties. The mechanical test results showed that the mechanical properties was reduced with the addition of BPS but improved with the addition of PC.

(2) The flame retardant mechanism of PET / PC / BPS blends was investigated in detail. The TGA and SEM tests showed that the addition of BPS promoted the formation of charcoal in advance during combustion. The carbon layer formed after combustion is complete, and uniformly dispersed honeycomb holes are observed obviously. TG-IR combined measurement showed that the flame retardation occurred prevailingly in the first stage of PET decomposition, the incorporation of BPS promoted effectively the decomposition of PC to generate a large amount of CO2 and exhibit a better gas phase flame retardant mechanism.

(3) The effect of amino silicone oil (ASO) on the flame retardancy and combustion behaviors of PET/PC/ASO blends was investigated. The flame retardant test results show that the flame-retarded blends passed UL94 V-0 testing at 0.5 phr loading level of ASO.  The cone calorimetry analysis showed that the occurrence time of the PHRR peak became later and lower with the increasing ASO loading level, the continuous exothermic process also became wider.

(4) The flame retardant mechanism of PET/PC/ASO blends was investigated in detail. Thermogravimetric analysis showed that the addition of ASO delayed the initial decomposition of the matrix, which promoted the decomposition rate and enhanced the strength of the carbon layer. The TG-IR test showed that the addition of ASO acted as gas phase flame retardant effect. Infrared spectra, SEM images and EDS analysis of the residual char showed that with the increase of flame retardant content, the matrix decomposed much completely during the combustion, more CO2 is produced, which played a role in gas phase flame retardant effect; At the same time, a high-strength carbon-silicon skeleton from the Si-C bond structure is formed on the surface of the substrate to act as a condensed phase flame retardant.

关键词:聚对苯二甲酸乙二醇酯;聚碳酸酯;高分子溴系阻燃剂;含硅阻燃剂;阻燃机理

Polyethylene terephthalate; Polycarbonate; Polymer bromine-containing flame retardant; Silicon-containing flame retardant; Flame retardant mechanism

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