氮硫硅协效阻燃剂的合成及在聚碳酸酯中的应用

Synthesis of Flame Retardant with Synergistic Effect of Nitrogen, Sulfur, and Silicon and Its Application in Polycarbonate

为研究氮硫硅元素间的协效阻燃作用,以三聚氯氰、氨基乙磺酸、对氨基苯酚和1,3-双(3-氨基丙基)四甲基二硅氧烷为原料,通过亲核取代反应制备了一种含氮硫硅的阻燃剂2,2’-(1,1,3,3-四甲基二硅氧烷-1,3-二基)双(丙烷-3,1-二基)-双(4-氨基乙磺酸钾-6-(4-(羟基苯基)氨基)-1,3,5-均三嗪)(KTS),并用熔融共混技术制备了聚碳酸酯(PC)/KTS复合材料。采用热重分析(TGA)、极限氧指数(LOI)、垂直燃烧(UL 94)及锥形量热(CONE)研究了复合材料的热稳定性和燃烧性能。结果表明,KTS的加入虽然降低了复合材料的热稳定性,但也促使复合材料提前分解成炭,抑制了材料的进一步分解;当KTS的质量分数为0.5%时,复合材料的LOI提高到34.6%,并通过了UL 94 V-0级;复合材料的热释放峰值和烟释放峰值分别降低了41.3%和35.3%。扫描电镜和拉曼光谱结果表明,KTS的加入提高了炭层的表面规整性和石墨化程度,起到良好的凝聚相阻燃作用。

Based on the synergistic effect of nitrogen,sulfur,and silicon on flame retardancy,a flame retardant containing nitrogen,sulfur,and silicon of 2,2′-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propane-3,1-diyl)-bis(potassium-4-aminoethanesulfonate-6-(4-(hydroxyphenyl)amino)-1,3,5-triazine)(KTS)was synthesized via the nucleophilic substitution reaction of cyanuric chloride,aminoethanesulfonic acid,p-aminophenol,1,3-bis(3-aminopropyl)-1,1,3,3,-tetramethyldisiloxane.The PC/KTS composites were prepared by melt blending.The thermal stability and flame retardancy of the composites were investigated by thermogravimetric analysis(TGA),limiting oxygen index(LOI),vertical combustion(UL 94)and cone calorimetry(CONE).The TGA results show that the incorporation of KTS promotes the decomposition and charring of the materials at a relative low temperature,and the further decomposition of the materials is restrained.Unfortunately,the thermal stability of the composites is decreased.In addition,when mixing with 0.5% KTS with PC,the flame retardancy of the materials is effectively changed,the LOI arrives at 34.60% and passes the UL 94 V-0 rating,and then the pk-HRR and pk-SPR of composites are reduced by 41.25% and 35.3%,respectively,compared with pure PC.The SEM and Raman spectra results indicate the introduction of KTS is more conducive to the formation of high surface regularity and high graphitization degree char layer on the surface of the inner materials,played a functional role in condensed phase flame retardancy.