阻燃剂有机硅酸单环膦酸酯的合成与应用
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摘要
以笼状亚磷酸酯4-乙基-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷和甲基三甲氧基硅烷为原料,合成一种有机硅磷协同效应的阻燃剂,即有机硅酸单环膦酸酯(MSAMP)。探究不同物质的量比、反应温度以及反应时间对产率的影响,得出最佳反应条件:n(笼状亚磷酸酯):n(甲基三甲氧基硅烷)=1:1.2,在反应温度155℃的条件下反应17h,产品得率为87.5%。通过FTIR、~1H-NMR、TG-DTA对产物的结构及性能进行了表征,将产物应用于191不饱和树脂和PBT,通过极限氧指数法来测试其阻燃性能。结果表明,该产物具有较好的热稳定性及良好的阻燃效果。
A phosphorus,silicon element dual synergistic flame retardant,methyldimethoxy silicic acid monocyclic phosphonate,was synthesized by caged phosphite-4-ethyl-2,6,7-trioxa-1-phosphorus oxabicyclo[2.2.2]octane and mthyltrimethoxysilane.The effects of different mass ratio,reaction temperature and reaction time on yield were investigated,and the best reaction conditions were obtained:With dimethyl sulfate as catalyst,n(cage phosphate):n(methyltrimethoxy silane)=1:1.2,and the reaction yield was 87.5%at 155℃ for 17 h.The structure of the product was characterized by FTIR,~1H-NMR and TG-DTA.The structure of the product was characterized by FTIR,~1H-NMR and TG-DTA.The flame retardancy was tested by limiting oxygen index to 191 unsaturated resin and PBT.The results show that the product has good thermal stability and shows good flame retardant effect.
A phosphorus,silicon element dual synergistic flame retardant,methyldimethoxy silicic acid monocyclic phosphonate,was synthesized by caged phosphite-4-ethyl-2,6,7-trioxa-1-phosphorus oxabicyclo[2.2.2]octane and mthyltrimethoxysilane.The effects of different mass ratio,reaction temperature and reaction time on yield were investigated,and the best reaction conditions were obtained:With dimethyl sulfate as catalyst,n(cage phosphate):n(methyltrimethoxy silane)=1:1.2,and the reaction yield was 87.5%at 155℃ for 17 h.The structure of the product was characterized by FTIR,~1H-NMR and TG-DTA.The structure of the product was characterized by FTIR,~1H-NMR and TG-DTA.The flame retardancy was tested by limiting oxygen index to 191 unsaturated resin and PBT.The results show that the product has good thermal stability and shows good flame retardant effect.
引文
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[3]夏俊,王良芥,罗和安.阻燃剂的发展现状和开发动向[J].应用化工,2005,34(1):1-4.
[4]周安安.有机硅阻燃剂协同阻燃作用的研究进展[J].有机硅材料,2005,19(6):28-31.
[5] Peng J,Hao J W,Du J X,et al.Flame retardancy and thermal properties of solid bisphenol A bis(diphenyl phosphste)combined with montmorillonite in polycarbonate[J].Polym Degard Stab,2010,(95):2041-2048.
[6]Sponnton M,Lligadas G,Ronda J C,et al.Development of a DOPO-containing benzoxazine and its high-performance flame retardant copolybenzoxazines[J].Polym Degard Stab,2009,94:1693-1699
[7]卢林刚,王会娅,杨守生,等.磷系阻燃剂杂环己内磷酸酯衍生物的合成及性能研究[J].化学研究与应用,2008,20(4):479-482.
[8]Li X,OU Y X,Zhang Y H,et al.Synthesis and strueture of a novel caged bicyclic phosphate flame retardant[J].Chin Chem Lett,2000,10:887-890.
[9]付晓丁,陈志林.环状磷酸酯类阻燃剂的研究进展[J].中国塑料,2011,25(2):19-23.
[10]杨挺,陈立强.国内外PBT树脂市场现状及未来发展趋势[J].塑料工业,2013,41(7):123-126.
[11]Baskaran R,Sarojadevi M,Vijayakumar C.Unsaturated polyester nanocomposites filled with nano alumina[J].J Mater Sci,2011,46,(14):4864-4871.
[12]张凤彦,不饱和聚酯树脂的新进展[J],河北化工,2006,29(3):57-58.