新型含氮阻燃剂的制备及应用研究
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摘要
膨胀型无卤阻燃技术已经成为近年来最为活跃的研究领域之一,三聚氰胺磷酸类盐阻燃剂是膨胀型阻燃剂发展比较快的一种。
本论文进行了无卤、含氮膨胀型阻燃剂的制备及其在防火涂料中的应用研究。(1)利用溶剂法制备了三聚氰胺磷酸盐(MP)、三聚氰胺焦磷酸盐(MPY)和三聚氰胺聚磷酸盐(MPOP),并用磷酸为原料代替传统的三氯氧磷制备了季戊四醇磷酸酯蜜胺盐(MPP),减少了污染物的排放,并通过对中间体-季戊四醇磷酸酯的制备及表征,推测出季戊四醇磷酸酯蜜胺盐(MPP)的结构及反应机理;(2)利用新颖的固相化学法制备了三聚氰胺聚磷酸盐(MPOP)和季戊四醇磷酸酯蜜胺盐(MPP),制备过程环保无污染;(3)本文考察了反应温度、反应时间及其原料比等条件对反应的影响,并通过单因素及正交实验得出溶剂法和固相化学法的较佳合成工艺;利用FT-IR、MS、NMR、TG、DSC等方法对产物的结构、热性能进行表征与测试,结果表明产物红外光谱图与文献基本一致,同时初步探究了其反应机理和阻燃机理。实验结果显示溶剂法制备季戊四醇磷酸酯蜜胺盐(MPP)的较佳原料摩尔比为n_(磷酸):n_(季戊四醇):n_(三聚氰胺)=2.5:1.0:2.0,第一步较佳反应温度为120℃,反应时间为4 h,第二步较佳反应温度为70℃,反应时间为4 h,其分解温度在240℃左右,在800℃时剩炭率为36%;固相化学法制备季戊四醇磷酸酯(MPP)适宜原料摩尔比为n_(五氧化二磷):n_(磷酸):n_(三聚氰胺):n_(季戊四醇)=2.0:1.0:2.1:1.0,反应温度为200℃较佳,较佳反应时间为4 h;(4)将各种含氮阻燃剂制备防火涂料,设计了防火涂料的配方及制备工艺,同时考察了防火涂料各种性能指标。结果表明季戊四醇磷酸酯蜜胺盐(MPP)制备的防火涂料的耐燃时间为39.5 min,其理化性也均优于国家标准,是一种性能优越的防火涂料。
Intumescent halogen-free flame retardant technology has become the one of the most active areas.Melamine phosphate salt is the type of intumescent flame retardant for a faster development.
This paper researched the preparation of halogen-free,nitrogen-containing intumescent flame retardants(IFR) and their application in fireproof coating.(1) Melamine phosphates (MP),melamine pyrophosphate(MPY) and melamine polyphosphate(MPOP) were prepared successfully in solvent.And in order to reduce the emission of pollutant,the intumescent flame retardant named melamine salt of pentaerythritol phosphate(MPP) was synthesized from phosphoric acid instead of phosphorus oxychloride(POCl_3) in the conventional technology.The intermediate- pentaerythritol phosphate was prepared and characterized to speculate the molecular structure and the reaction mechanism of melamine salt of pentaerythritol phosphate(MPP).(2) The melamine polyphosphate(MPOP) and melamine salt of pentaerythritol phosphate(MPP) were further prepared in solid-phase.The preparation process was no pollution.(3) The effects of reaction temperature,time and molar ratio on each reaction were discussed in this paper.The optimum synthetic conditions in solvent and in solid were obtained from single factor experiments and orthogonal experiments.The structure and thermal behaviors were characterized and studied by FT-IR、MS、NMR、TG-DTA and DSC respectively,the IR spectrum of the products showed that they were basically consistent with the literature,and the reaction mechanism and the flame-retardant mechanism were discussed.The result showed that the optimum molar ratio of phosphoric acid,pentaerythritol and melamine in the preparation of melamine salt of pentaerythritol phosphate(MPP) in solvent was 2.5:1.0:2.0,and its reaction temperature and time in the first step were 120℃and 4 h respectively.And the reaction temperature and time in the second step were 70℃and 4 h respectively.It started melting and degrading at about 240℃, and the char yield could reach 36%at 800℃.The optimum molar ratio of P_2O_5,H_3PO_4, melamine and pentaerythritol in the preparation of melamine salt of pentaerythritol phosphate (MPP) in soild was 2.0:1.0:2.1:1.0,and the reaction temperature and time were 200℃and 4 h respectively.(4)Then the products were applicated in fireproof coating,the molar ratio and preparation process were designed,and a variety of performance of the coating was also studied.The result showed that the limited time of fire-endurance of fireproof coating containing melamine salt of pentaerythritol phosphate(MPP) was 39.5min,and its performance also better than the national standards,which showed that such a coating was an excellent fireproof coating.
本论文进行了无卤、含氮膨胀型阻燃剂的制备及其在防火涂料中的应用研究。(1)利用溶剂法制备了三聚氰胺磷酸盐(MP)、三聚氰胺焦磷酸盐(MPY)和三聚氰胺聚磷酸盐(MPOP),并用磷酸为原料代替传统的三氯氧磷制备了季戊四醇磷酸酯蜜胺盐(MPP),减少了污染物的排放,并通过对中间体-季戊四醇磷酸酯的制备及表征,推测出季戊四醇磷酸酯蜜胺盐(MPP)的结构及反应机理;(2)利用新颖的固相化学法制备了三聚氰胺聚磷酸盐(MPOP)和季戊四醇磷酸酯蜜胺盐(MPP),制备过程环保无污染;(3)本文考察了反应温度、反应时间及其原料比等条件对反应的影响,并通过单因素及正交实验得出溶剂法和固相化学法的较佳合成工艺;利用FT-IR、MS、NMR、TG、DSC等方法对产物的结构、热性能进行表征与测试,结果表明产物红外光谱图与文献基本一致,同时初步探究了其反应机理和阻燃机理。实验结果显示溶剂法制备季戊四醇磷酸酯蜜胺盐(MPP)的较佳原料摩尔比为n_(磷酸):n_(季戊四醇):n_(三聚氰胺)=2.5:1.0:2.0,第一步较佳反应温度为120℃,反应时间为4 h,第二步较佳反应温度为70℃,反应时间为4 h,其分解温度在240℃左右,在800℃时剩炭率为36%;固相化学法制备季戊四醇磷酸酯(MPP)适宜原料摩尔比为n_(五氧化二磷):n_(磷酸):n_(三聚氰胺):n_(季戊四醇)=2.0:1.0:2.1:1.0,反应温度为200℃较佳,较佳反应时间为4 h;(4)将各种含氮阻燃剂制备防火涂料,设计了防火涂料的配方及制备工艺,同时考察了防火涂料各种性能指标。结果表明季戊四醇磷酸酯蜜胺盐(MPP)制备的防火涂料的耐燃时间为39.5 min,其理化性也均优于国家标准,是一种性能优越的防火涂料。
Intumescent halogen-free flame retardant technology has become the one of the most active areas.Melamine phosphate salt is the type of intumescent flame retardant for a faster development.
This paper researched the preparation of halogen-free,nitrogen-containing intumescent flame retardants(IFR) and their application in fireproof coating.(1) Melamine phosphates (MP),melamine pyrophosphate(MPY) and melamine polyphosphate(MPOP) were prepared successfully in solvent.And in order to reduce the emission of pollutant,the intumescent flame retardant named melamine salt of pentaerythritol phosphate(MPP) was synthesized from phosphoric acid instead of phosphorus oxychloride(POCl_3) in the conventional technology.The intermediate- pentaerythritol phosphate was prepared and characterized to speculate the molecular structure and the reaction mechanism of melamine salt of pentaerythritol phosphate(MPP).(2) The melamine polyphosphate(MPOP) and melamine salt of pentaerythritol phosphate(MPP) were further prepared in solid-phase.The preparation process was no pollution.(3) The effects of reaction temperature,time and molar ratio on each reaction were discussed in this paper.The optimum synthetic conditions in solvent and in solid were obtained from single factor experiments and orthogonal experiments.The structure and thermal behaviors were characterized and studied by FT-IR、MS、NMR、TG-DTA and DSC respectively,the IR spectrum of the products showed that they were basically consistent with the literature,and the reaction mechanism and the flame-retardant mechanism were discussed.The result showed that the optimum molar ratio of phosphoric acid,pentaerythritol and melamine in the preparation of melamine salt of pentaerythritol phosphate(MPP) in solvent was 2.5:1.0:2.0,and its reaction temperature and time in the first step were 120℃and 4 h respectively.And the reaction temperature and time in the second step were 70℃and 4 h respectively.It started melting and degrading at about 240℃, and the char yield could reach 36%at 800℃.The optimum molar ratio of P_2O_5,H_3PO_4, melamine and pentaerythritol in the preparation of melamine salt of pentaerythritol phosphate (MPP) in soild was 2.0:1.0:2.1:1.0,and the reaction temperature and time were 200℃and 4 h respectively.(4)Then the products were applicated in fireproof coating,the molar ratio and preparation process were designed,and a variety of performance of the coating was also studied.The result showed that the limited time of fire-endurance of fireproof coating containing melamine salt of pentaerythritol phosphate(MPP) was 39.5min,and its performance also better than the national standards,which showed that such a coating was an excellent fireproof coating.
引文
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[7]欧育湘.国外阻燃剂发展动态及对我国阻燃剂工业之浅见[J].精细与专品,2003,2:3-6.
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[9]史翎.段雪.阻燃剂的发展及在塑料中的应用[J].塑料,2002,31(3):11-15.
[10]Lu S Y,Hmaerton L.Recent developments in the chemistry of halogen- free flame retardant polymers[J].Polymer Sciences,2002,27:1661-1712.
[11]杨娜,徐晓楠.我国溴系阻燃剂生产结构、发展新动向[J].消防技术与产品信息,2004.4:56-58.
[12]欧育湘.实用阻燃技术[M].北京:化学工业出版社,2001:133-135.
[13]王晓栋.环保型阻燃剂的研究发展[J].化学工程师,2006,3:33-35.
[14]郑宝贤.氢氧化铝制备方法进展[J].无机盐工业,1991,5:11-14.
[15]Hong B L,Anila A,Wen F S.Thermal degradation and flame retardancy of a novel methacrylated phenolic melamine used for UV curable flame retardant coatings[J].Polymer Degradation and Stability,2005,87:495-501.
[16]欧育湘.阻燃剂-制造、性能及应用[M].北京:兵器工业出版社,1997:139-147.
[17]刘颖.双组分膨胀型透明防火涂料的性能探究[J].材料保护,1993,26(8):33-35.
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