丁胺封端三嗪成炭剂对聚丙烯的阻燃作用
|
摘要
通过极限氧指数(LOI)测定,垂直燃烧试验和锥形量热分析研究了丁胺封端三嗪成炭剂(成炭剂-2)对聚丙烯(PP)的阻燃作用,并与未封端的三嗪成炭剂(成炭剂-1)进行了比较。结果表明,由成炭剂-1和成炭剂-2与聚磷酸铵(APP)复配而成的膨胀型阻燃剂(分别简称IFR-1和IFR-2)对PP均具有良好的阻燃作用。垂直燃烧试验和LOI测定表明,IFR-1和IFR-2的阻燃作用无明显差异;而锥形量热试验表明,IFR-2的阻燃作用好于IFR-1。锥形量热试验残余物分析表明,APP受热分解形成的聚偏磷酸促使成炭剂脱水炭化,并在APP、成炭剂和PP分解过程中产生的惰性气体作用下膨胀发泡,形成致密的膨胀性炭层。该膨胀性炭层通过隔热、隔氧和阻止裂解物挥发而产生阻燃作用。丁胺封端有效地降低了成炭剂的氯含量,并显著改善了其热稳定性,这使成炭剂更能满足阻燃材料无卤的要求,并有利于改善塑料加工的环境和防止加工设备的腐蚀。
The flame retardancy of triazine charring agent terminated with butylamine(charring agent-2) in polypropylene(PP) was studied by limiting oxygen index(LOI) measurement, vertical burning test and cone calorimetry test, with non-terminated charring agent(Charring agent-1) as comparison. It is shown that the intumescent flame retardants(IFR-1 and IFR-2), which respectively is composed of charring agent-1, charring agent-2 and ammonium polyphosphate(APP), have good flame retardancy in PP. The flame retardancy of IFR-1 and IFR-2 has no significant difference from the results of the vertical burning test and LOI, while the flame retardance of IFR-2 is better than that of IFR-1 from the results of the cone calorimetry test. It is shown from the analysis of the residue obtained in CCT that polymetaphosphoric acid from the decompostion of APP in the process of combustion promotes the dehydrateion and carbonization of charring agent, and the char is changed into the intumescent layer by the foaming of inert gases released from the decomposition of APP, charring agent and PP. The flame retardant effect is consequently resulted from the intumescent layer through heat and oxygen insulation, prevention of pyrolysis volatilization as well. The chlorine content of charring agent is effectively reduced and the thermal stability is markedly improved when the charring agent is terminated with butylamine, which makes it meet the halogen-free requirements of flame-retarded products better, is in favor of improving the environment of plastic processing, and prevents the corrosion of processing equipments.
The flame retardancy of triazine charring agent terminated with butylamine(charring agent-2) in polypropylene(PP) was studied by limiting oxygen index(LOI) measurement, vertical burning test and cone calorimetry test, with non-terminated charring agent(Charring agent-1) as comparison. It is shown that the intumescent flame retardants(IFR-1 and IFR-2), which respectively is composed of charring agent-1, charring agent-2 and ammonium polyphosphate(APP), have good flame retardancy in PP. The flame retardancy of IFR-1 and IFR-2 has no significant difference from the results of the vertical burning test and LOI, while the flame retardance of IFR-2 is better than that of IFR-1 from the results of the cone calorimetry test. It is shown from the analysis of the residue obtained in CCT that polymetaphosphoric acid from the decompostion of APP in the process of combustion promotes the dehydrateion and carbonization of charring agent, and the char is changed into the intumescent layer by the foaming of inert gases released from the decomposition of APP, charring agent and PP. The flame retardant effect is consequently resulted from the intumescent layer through heat and oxygen insulation, prevention of pyrolysis volatilization as well. The chlorine content of charring agent is effectively reduced and the thermal stability is markedly improved when the charring agent is terminated with butylamine, which makes it meet the halogen-free requirements of flame-retarded products better, is in favor of improving the environment of plastic processing, and prevents the corrosion of processing equipments.
引文
[1] Chen B, Gao W, Shen J, et al. The multilayered distribution of intumescent flame retardants and its influence on the fire and mechanical properties of polypropylene[J]. Compos. Sci. Technol., 2014, 93: 54-60.
[2] Enescu D, Frache A, Lavaselli M, et al. Novel phosphorous-nitrogen intumescent flame retardant system. Its effects on flame retardancy and thermal properties of polypropylene[J]. Polym. Degrad. Stab., 2013, 98: 297-305.
[3] Feng C, Zhang Y, Liu S, et al. Synthesis of novel triazine charring agent and its effect in intumescent flame-retardant polypropylene[J]. J. Appl. Polym. Sci., 2012, 123: 3208-3216.
[4] Feng C, Liang M, Jiang J, et al. Synergistic effect of a novel triazine charring agent and ammonium polyphosphate on the flame retardant properties of halogen-free flame retardant polypropylene composites[J]. Thermochim. Acta, 2016, 627/628/629: 83-90.
[5] Wang Y, Xu M J, Li B, et al. Synthesis of N-methyl triazine-ethylenediamine copolymer charring foaming agent and its enhancement on flame retardancy and water resistance for polypropylene composites[J]. Polym. Degrad. Stab., 2016, 131: 20-29.
[6] 唐霜, 尹昌宇, 赖学军,等. 三嗪类大分子成炭剂的合成及其在聚丙烯中应用[J]. 现代塑料加工应用, 2012, 24(4): 46-49.Tang S, Yin C Y, Lai X J, et al. Synthesis of triazine-based macromolecule charring agent and its application to polypropylene[J]. Modern Plastics Processing and Applications, 2012, 24(4): 46-49.
[7] Feng C, Zhang Y, Liu S, et al. Synthesis of novel triazine charring agent and its effect in intumescent flame-retardant polypropylene[J]. J. Appl. Polym. Sci., 2012, 123: 3208-3216.
[8] Feng C, Liang M, Jiang J, et al. Synergistic effect of ammonium polyphosphate and triazine-based charring agent on the flame retardancy and combustion behavior of ethylene-vinyl acetate copolymer[J]. J. Anal. Appl. Pyrolysis, 2016, 119: 259-269.
[9] Chen L, Yuan Y, Wang B, et al. Synthesis and application of novel triazine-based charring-foaming agents in intumescent flame retardant polypropylene[J]. Trans. Tianjin Univ., 2017, 23: 221-229.
[10] 胡亚鹏, 王香梅, 李娟. 多羟基结构三嗪成炭剂在膨胀阻燃PP中的应用[J]. 工程塑料应用, 2016, 44(6): 99-103.Hu Y P, Wang X M, Li J. Application of triazine-based charring agent with multi-hydroxyl group in intumescent flame retardant polypropylene[J]. Engineering Plastics Application, 2016, 44(6): 99-103.
[11] Wen P, Wang X, Wang B, et al. One-pot synthesis of a novel s-triazine-based hyperbranched charring foaming agent and its enhancement on flame retardancy and water resistance of polypropylene[J].Polym. Degrad. Stab., 2014, 110: 165-174.
[2] Enescu D, Frache A, Lavaselli M, et al. Novel phosphorous-nitrogen intumescent flame retardant system. Its effects on flame retardancy and thermal properties of polypropylene[J]. Polym. Degrad. Stab., 2013, 98: 297-305.
[3] Feng C, Zhang Y, Liu S, et al. Synthesis of novel triazine charring agent and its effect in intumescent flame-retardant polypropylene[J]. J. Appl. Polym. Sci., 2012, 123: 3208-3216.
[4] Feng C, Liang M, Jiang J, et al. Synergistic effect of a novel triazine charring agent and ammonium polyphosphate on the flame retardant properties of halogen-free flame retardant polypropylene composites[J]. Thermochim. Acta, 2016, 627/628/629: 83-90.
[5] Wang Y, Xu M J, Li B, et al. Synthesis of N-methyl triazine-ethylenediamine copolymer charring foaming agent and its enhancement on flame retardancy and water resistance for polypropylene composites[J]. Polym. Degrad. Stab., 2016, 131: 20-29.
[6] 唐霜, 尹昌宇, 赖学军,等. 三嗪类大分子成炭剂的合成及其在聚丙烯中应用[J]. 现代塑料加工应用, 2012, 24(4): 46-49.Tang S, Yin C Y, Lai X J, et al. Synthesis of triazine-based macromolecule charring agent and its application to polypropylene[J]. Modern Plastics Processing and Applications, 2012, 24(4): 46-49.
[7] Feng C, Zhang Y, Liu S, et al. Synthesis of novel triazine charring agent and its effect in intumescent flame-retardant polypropylene[J]. J. Appl. Polym. Sci., 2012, 123: 3208-3216.
[8] Feng C, Liang M, Jiang J, et al. Synergistic effect of ammonium polyphosphate and triazine-based charring agent on the flame retardancy and combustion behavior of ethylene-vinyl acetate copolymer[J]. J. Anal. Appl. Pyrolysis, 2016, 119: 259-269.
[9] Chen L, Yuan Y, Wang B, et al. Synthesis and application of novel triazine-based charring-foaming agents in intumescent flame retardant polypropylene[J]. Trans. Tianjin Univ., 2017, 23: 221-229.
[10] 胡亚鹏, 王香梅, 李娟. 多羟基结构三嗪成炭剂在膨胀阻燃PP中的应用[J]. 工程塑料应用, 2016, 44(6): 99-103.Hu Y P, Wang X M, Li J. Application of triazine-based charring agent with multi-hydroxyl group in intumescent flame retardant polypropylene[J]. Engineering Plastics Application, 2016, 44(6): 99-103.
[11] Wen P, Wang X, Wang B, et al. One-pot synthesis of a novel s-triazine-based hyperbranched charring foaming agent and its enhancement on flame retardancy and water resistance of polypropylene[J].Polym. Degrad. Stab., 2014, 110: 165-174.