反应型含磷多元醇/APP复配阻燃聚氨酯泡沫的制备及性能
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摘要
以非丁基氧化锡为催化剂,通过甲基膦酸二甲酯(DMMP)与乙二醇(EG)酯交换反应,制备了含磷多元醇(DMMP-EG)。将DMMP-EG与聚磷酸铵(APP)作为复合阻燃剂,制备了阻燃硬质聚氨酯泡沫(RPUF),探讨了复配阻燃剂对RPUF力学性能、阻燃性能、热稳定性的影响。结果表明:DMMP-EG与APP复配阻燃RPUF,在提高阻燃性能的同时,力学性能显著提高;当DMMP-EG添加15份、APP添加30份时,泡沫的力学性能最佳,与纯RPUF相比,压缩强度提高了1.25%,冲击强度提高了101.53%;此时,极限氧指数(LOI)提高至21.7%,烟密度等级为40。热重(TG)分析结果表明:在氮气气氛中,750℃时的残炭率较纯RPUF提高了612.56%。阻燃体系呈现以凝聚相为主的气相-凝聚相双相阻燃特点。
The phosphorus-containing polyol(DMMP-EG) was prepared by transesterification of dimethyl methylphosphonate(DMMP) with ethylene glycol(EG) using non-butyltin oxide as a catalyst. Flame retardant rigid polyurethane foam(RPUF) was prepared by using DMMP-EG and APP as composite flame retardants. The effects of compound flame retardants on mechanical properties, flame retardancy and thermal stability of RPUF were discussed. The results show that the flame retardant RPUF blended with DMMP-EG and APP can improve the flame retardant properties and mechanical properties significantly. When DMMP-EG is added to 15 phr and APP is added to 30 phr, the mechanical properties of the foam are the best. Compared with pure RPUF, the compressive strength increases by 1.25%, and the impact strength increases by 101.53%. At this time, the limiting oxygen index(LOI) increases to 21.7% and the smoke density level is 40. The thermogravimetric(TG) test showes that in nitrogen atmosphere, the carbon residue at 750℃ is 612.56% higher than that of pure RPUF. The flame retardant system exhibits the characteristics of gas-condensate biphasic flame retardant.
The phosphorus-containing polyol(DMMP-EG) was prepared by transesterification of dimethyl methylphosphonate(DMMP) with ethylene glycol(EG) using non-butyltin oxide as a catalyst. Flame retardant rigid polyurethane foam(RPUF) was prepared by using DMMP-EG and APP as composite flame retardants. The effects of compound flame retardants on mechanical properties, flame retardancy and thermal stability of RPUF were discussed. The results show that the flame retardant RPUF blended with DMMP-EG and APP can improve the flame retardant properties and mechanical properties significantly. When DMMP-EG is added to 15 phr and APP is added to 30 phr, the mechanical properties of the foam are the best. Compared with pure RPUF, the compressive strength increases by 1.25%, and the impact strength increases by 101.53%. At this time, the limiting oxygen index(LOI) increases to 21.7% and the smoke density level is 40. The thermogravimetric(TG) test showes that in nitrogen atmosphere, the carbon residue at 750℃ is 612.56% higher than that of pure RPUF. The flame retardant system exhibits the characteristics of gas-condensate biphasic flame retardant.
引文
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[20]张琪,刘娟,孙立婧,等.APP对硬质聚氨酯-酰亚胺泡沫泡孔结构及力学性能的影响[J].塑料,2015,44(5):7-10.
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[25]Zhu S W,Shi W F.Flame retardant mechanism of hyperbranched polyurethane acrylates used for UV curable flame retardant coatings[J].Polym Degrad Stabil,2002,75(3):543-547.
[2]Shen M Y,Chen W J,Kuan C F,et al.Preparation,characterization of microencapsulated ammonium polyphosphate and its flame retardancy in polyurethane composites[J].Mater Chem Phys,2016,173:205-212.
[3]Shi X,Jiang S,Zhu J,et al.Establishment of a highly efficient flame-retardant system for rigid polyurethane foams based on bi-phase flame-retardant actions[J].RSC Adv,2018,8(18):9 985-9 995.
[4]孙才英,董子琳,董懿嘉,等.阻燃剂甲基膦酸二甲酯对硬质聚氨酯泡沫性能的影响[J].塑料科技,2017,45(3):90-94.
[5]任强,丁晨,宋艳,等.羟基锡酸锌协同聚磷酸铵阻燃硬质聚氨酯泡沫[J].高分子材料科学与工程,2015,31(9):76-81.
[6]张晓光,孟现燕,叶玲,等.偶联剂处理聚磷酸铵/硬质聚氨酯泡沫[J].化工进展,2010,29(6):1 107-1 111.
[7]Gaan S,Liang S,Mispreuve H,et al.Flame retardant flexible polyurethane foams from novel DOPO-phosphonamidate additives[J].Polym Degrad Stabil,2015,113:180-188.
[8]丁海阳,王基夫,王春鹏,等.阻燃型聚氨酯泡沫的制备及性能研究[J].热固性树脂,2017(1):39-43.
[9]Rao W H,Xu H X,Xu Y J,et al.Persistently flame-retardant flexible polyurethane foams by a novel phosphoruscontaining polyol[J].Chem Eng J,2018,343:198-206.
[10]闫莉,刘娟,李青芳,等.含磷本质阻燃硬质聚氨酯泡沫塑料的制备及性能[J].高分子材料科学与工程,2017,33(7):6-10.
[11]Rao W H,Zhu Z M,Wang S X,et al.A reactive phosphoruscontaining polyol incorporated into flexible polyurethane foam:Self-extinguishing behavior and mechanism[J].Polym Degrad Stabil,2018,153:192-200.
[12]Luo F,Wu K,Lu M,et al.Thermal degradation and flame retardancy of microencapsulated ammonium polyphosphate in rigid polyurethane foam[J].J Therm Anal Calorim,2015,120(2):1 327-1 335.
[13]Xi W,Qian L,Huang Z,et al.Continuous flame-retardant actions of two phosphate esters with expandable graphite in rigid polyurethane foams[J].Polym Degrad Stabil,2016,130:97-102.
[14]Zhao B,Liu D Y,Liang W J,et al.Bi-phase flame-retardant actions of water-blown rigid polyurethane foam containing diethyl-N,N-bis(2-hydroxyethyl)phosphoramide and expandable graphite[J].J Anal Appl Pyrol,2017,124:247-255.
[15]杨荣,乔红,胡文田,等.反应型磷氮阻燃剂/可膨胀石墨复配阻燃聚氨酯泡沫[J].化工学报,2016,67(5):2 169-2 175.
[16]孙惠惠.含磷环氧树脂的合成与性能研究[D].北京:北京化工大学,2012.
[17]杨宏宇.硬质聚氨酯泡沫的含磷阻燃体系研究[D].合肥:中国科学技术大学,2015.
[18]王新轲,陈亚洪,王贵友.阻燃多元醇的合成及在聚氨酯泡沫中的应用[J].高分子材料科学与工程,2015,31(6):27-33.
[19]王晋,纪双英,郝春鹏,等.成核剂对聚氨酯泡沫成核性能的影响[J].化学推进剂与高分子材料,2009,7(5):41-43.
[20]张琪,刘娟,孙立婧,等.APP对硬质聚氨酯-酰亚胺泡沫泡孔结构及力学性能的影响[J].塑料,2015,44(5):7-10.
[21]Herrera M,Matuschek G,Kettrup A.Thermal degradation of thermoplastic polyurethane elastomers(TPU)based on MDI[J].Polym Degrad Stabil,2002,78(2):323-331.
[22]袁开军,江治,李疏芬,等.聚氨酯的热分解研究进展[J].高分子材料科学与工程,2005,21(4):51-54.
[23]Duquesne S,Bras M L,Bourbigot S,et al.Thermal degradation of polyurethane and polyurethane/expandable graphite coatings[J].Polym Degrad Stabil,2001,74(3):493-499.
[24]Yoshitake N,Furukawa M.Thermal degradation mechanism ofα,γ-diphenyl alkyl allophanate as a model polyurethane by pyrolysis-high-resolution gas chromatography/FT-IR[J].JAnal Appl Pyrol,1995,33(3):269-281.
[25]Zhu S W,Shi W F.Flame retardant mechanism of hyperbranched polyurethane acrylates used for UV curable flame retardant coatings[J].Polym Degrad Stabil,2002,75(3):543-547.