含氮反应型阻燃剂的制备及对聚氨酯泡沫阻燃性能的影响
|
摘要
采用三聚氰胺和甲醛合成了一种含氮反应型阻燃剂多羟甲基三聚氰胺(HM),通过FTIR对其结构进行了表征,并通过热重分析考察了该阻燃剂的热降解机理。将HM与甲基磷酸二甲酯(DMMP)复配后用于阻燃聚氨酯泡沫塑料(PUF)的制备,通过极限氧指数(LOI)测试、垂直燃烧测试、热重分析及炭层形貌分析对PUF的阻燃性能和热性能进行了研究。结果表明:成功合成了目标产物HM,其初始分解温度为150℃,800℃残炭率为18.37%。复配阻燃剂HM-DMMP的加入能有效改善PUF的阻燃性能,其中当HM及DMMP的添加量分别为35%和12%时,可以获得综合性能较好的PUF材料,其LOI从纯PUF的18.1%提高到27.5%、垂直燃烧等级达到UL 94V-0级,同时最大热降解速率较之纯PUF显著下降,800℃残炭率达到19.87%;HM的加入不会对PUF的力学性能造成影响,但是HM-DMMP复配阻燃剂的加入使得PUF的压缩强度与冲击强度略有下降。炭层SEM分析结果表明,阻燃剂的加入使PUF的阻燃性能得到较大改善。
A nitrogen-containing reactive flame retardant, Hydroxy methyl melamine(HM), was obtained by melaine and formaldehyde. The structure was characterized by FTIR and the thermal degradation mechanism was analyzed by TGA. The HM and dimethyl methyl phosphonate(DMMP) were compounded to prepare flame-retardant polyurethane foams(PUF), and the flame retardant properties and the thermal performance of the PUFs were tested by limited oxygen index(LOI), the vertical burning test, TGA and char layer morphology. The results show that HM is successfully obtained, and the initial degradation temperature of HM is 150℃, and the residual carbon rate at 800℃ is 18.37%. At a content of 35% HM and 12% DMMP, the flame retardant PUF with better comprehensive performance can be obtained, and the LOI is improved from 18.1% to 27.5%, UL 94 vertical burning rate reaches V-0, while the maximum thermal degradation rate decreases significantly, and the residual carbon rate at 800℃ is 19.87%. The addition of HM has no effect on the mechanical properties of PUF, but the addition of HM-DMMP compound flame retardant results in a slight decrease in compressive strength and impact strength. Through the SEM of the char layer, it is proved that the addition of the flame retardant has greatly improved the flame retardancy of PUF.
A nitrogen-containing reactive flame retardant, Hydroxy methyl melamine(HM), was obtained by melaine and formaldehyde. The structure was characterized by FTIR and the thermal degradation mechanism was analyzed by TGA. The HM and dimethyl methyl phosphonate(DMMP) were compounded to prepare flame-retardant polyurethane foams(PUF), and the flame retardant properties and the thermal performance of the PUFs were tested by limited oxygen index(LOI), the vertical burning test, TGA and char layer morphology. The results show that HM is successfully obtained, and the initial degradation temperature of HM is 150℃, and the residual carbon rate at 800℃ is 18.37%. At a content of 35% HM and 12% DMMP, the flame retardant PUF with better comprehensive performance can be obtained, and the LOI is improved from 18.1% to 27.5%, UL 94 vertical burning rate reaches V-0, while the maximum thermal degradation rate decreases significantly, and the residual carbon rate at 800℃ is 19.87%. The addition of HM has no effect on the mechanical properties of PUF, but the addition of HM-DMMP compound flame retardant results in a slight decrease in compressive strength and impact strength. Through the SEM of the char layer, it is proved that the addition of the flame retardant has greatly improved the flame retardancy of PUF.
引文
[1]张汪强,郭刚,邱进俊,等.反应型含磷阻燃多元醇制备聚氨酯硬泡及性能[J].高分子材料科学与工程,2015,31(9):142-146.
[2]倪旭萍.阻燃聚氨酯相变储能材料的制备及其火灾行为的研究[D].成都:西南交通大学,2015.
[3]F F Feng,L J Qian.The flame retardant behaviors and synergistic effect of expandable graphite and dimethyl methylphosphonate in rigid polyurethane foams[J].Polymer Composites,2014,35(2):301-309.
[4]Y T Wang,F Wang,Q X Dong.Core-shell expandable graphite@aluminum hydroxide as a ame-retardant for rigid polyurethane foams[J].Polymer Degradation and Stability,2017,146:267-276.
[5]徐娜,尤勇军,陆敏,等.反应型阻燃聚醚多元醇的合成及应用[J].热固性树脂,2017,32(4):20-28.
[6]李艳,贾积恒,田盛益,等.含磷阻燃聚醚多元醇的制备及其在聚氨酯硬泡中的应用[J].2016,31(1):25-28.
[7]宋艳,许亮,李锦春,等.新型磷氮型阻燃剂的制备及其阻燃聚氨酯泡沫塑料[J].复合材料学报,2016,33(11):2 461-2 467.
[8]R Yang,B Wang,X F Wang,et al.Synthesis and characteriation of flame retardant rigid polyurethane foam based on a reactive ame retardant containing phosphazene and cyclophosphonate[J].Polymer Degradation and Stability,2017,144:62-67.
[9]Y Yuan,C Ma,Y Q Shi,et al.Highly-ef cient reinforcement and flame retardancy of rigid polyurethane foam with phosphorus-containing additive and nitrogen-containing compound[J].Materials Chemistry and Physics,2018,211:42-53.
[10]H Y Ding,K Huang,S H Li,et al.Synthesis of a novel phosphorus and nitrogen-containing bio-based poluol and its application in ame retardant polyurethane foam[J].Journal of Analytical and Applied Pyrolysis,2017,128:102-113.
[11]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.
[12]魏路.三聚氰胺本征结构阻燃聚醚多元醇的合成及其聚氨酯硬质泡沫体系研究[D].上海:上海应用技术学院,2015.
[13]国家标准化管理委员会.GB/T 8813-2008硬质泡沫塑料压缩性能的测定[S].北京:中国标准出版社,2008.
[14]国家标准化管理委员会.GB/T 13525-1992塑料拉伸冲击性能试验方法[S].北京:中国标准出版社,1992.
[15]国家标准化管理委员会.GB/T 6364-2009泡沫塑料及橡胶表观密度的测定[S].北京:中国标准出版社,2009.
[16]国家标准化管理委员会.GB/T 2406-1993塑料燃烧性能试验方法氧指数法[S].北京:中国标准出版社,1993.
[17]国家标准化管理委员会.GB/T 8333-2008硬质泡沫塑料燃烧性能试验方法垂直燃烧法[S].北京:中国标准出版社,2008.
[18]李建军,欧育湘.阻燃理论[M].北京:科学出版社,2013.
[19]刘益军.聚氨酯树脂及其应用[M].北京:化学工业出版社,2011.
[2]倪旭萍.阻燃聚氨酯相变储能材料的制备及其火灾行为的研究[D].成都:西南交通大学,2015.
[3]F F Feng,L J Qian.The flame retardant behaviors and synergistic effect of expandable graphite and dimethyl methylphosphonate in rigid polyurethane foams[J].Polymer Composites,2014,35(2):301-309.
[4]Y T Wang,F Wang,Q X Dong.Core-shell expandable graphite@aluminum hydroxide as a ame-retardant for rigid polyurethane foams[J].Polymer Degradation and Stability,2017,146:267-276.
[5]徐娜,尤勇军,陆敏,等.反应型阻燃聚醚多元醇的合成及应用[J].热固性树脂,2017,32(4):20-28.
[6]李艳,贾积恒,田盛益,等.含磷阻燃聚醚多元醇的制备及其在聚氨酯硬泡中的应用[J].2016,31(1):25-28.
[7]宋艳,许亮,李锦春,等.新型磷氮型阻燃剂的制备及其阻燃聚氨酯泡沫塑料[J].复合材料学报,2016,33(11):2 461-2 467.
[8]R Yang,B Wang,X F Wang,et al.Synthesis and characteriation of flame retardant rigid polyurethane foam based on a reactive ame retardant containing phosphazene and cyclophosphonate[J].Polymer Degradation and Stability,2017,144:62-67.
[9]Y Yuan,C Ma,Y Q Shi,et al.Highly-ef cient reinforcement and flame retardancy of rigid polyurethane foam with phosphorus-containing additive and nitrogen-containing compound[J].Materials Chemistry and Physics,2018,211:42-53.
[10]H Y Ding,K Huang,S H Li,et al.Synthesis of a novel phosphorus and nitrogen-containing bio-based poluol and its application in ame retardant polyurethane foam[J].Journal of Analytical and Applied Pyrolysis,2017,128:102-113.
[11]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.
[12]魏路.三聚氰胺本征结构阻燃聚醚多元醇的合成及其聚氨酯硬质泡沫体系研究[D].上海:上海应用技术学院,2015.
[13]国家标准化管理委员会.GB/T 8813-2008硬质泡沫塑料压缩性能的测定[S].北京:中国标准出版社,2008.
[14]国家标准化管理委员会.GB/T 13525-1992塑料拉伸冲击性能试验方法[S].北京:中国标准出版社,1992.
[15]国家标准化管理委员会.GB/T 6364-2009泡沫塑料及橡胶表观密度的测定[S].北京:中国标准出版社,2009.
[16]国家标准化管理委员会.GB/T 2406-1993塑料燃烧性能试验方法氧指数法[S].北京:中国标准出版社,1993.
[17]国家标准化管理委员会.GB/T 8333-2008硬质泡沫塑料燃烧性能试验方法垂直燃烧法[S].北京:中国标准出版社,2008.
[18]李建军,欧育湘.阻燃理论[M].北京:科学出版社,2013.
[19]刘益军.聚氨酯树脂及其应用[M].北京:化学工业出版社,2011.