含磷阻燃剂阻燃聚氨酯的研究进展
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摘要
含磷阻燃剂由于其高效、无卤低毒等优点,成为阻燃研究领域的关注热点之一。P元素氧化价态不同,对应的含磷阻燃剂的阻燃机理就不同,并且其对聚氨酯材料阻燃性能的影响也有差异。根据P元素的氧化价态,将含磷阻燃剂分成红磷(0价)、亚膦酸酯和次膦酸盐(+1价)、膦酸酯和膦酸盐(+3价)以及磷酸酯和磷酸盐(+5价)四类,对每种价态所对应的典型含磷阻燃剂特点和阻燃机理进行了简要概述。详细综述了每种价态所对应的典型含磷阻燃剂在聚氨酯材料中的应用研究进展以及将2种或几种不同价态含磷阻燃剂复配阻燃聚氨酯的研究进展。最后,针对目前含磷阻燃剂阻燃聚氨酯存在的问题,提出了含磷阻燃剂在聚氨酯阻燃领域应用中的研究思路。
Phosphorus-containing flame retardants with the advantages of high efficiency,no halogen and low toxicity are becoming one of the most important research branches in the field of flame retardant,which mainly focus on the research of synthesis and application of phosphorus-containing flame retardants. The phosphorus-containing flame retardants with different oxidation state of phosphorus have different flame retardant mechanism and different flame retardancy effect on polyurethane.The phosphorus-containing flame retardants are classified by the different oxidation state of phosphorus in four categories,which include red phosphorus( + 0),phosphite and hypophosphite( + 1),phosphonate( + 3) and phosphate( + 5). The feature and flame retardant mechanism are reviewed. Research progress on the application of the typical phosphorus-containing flame retardants corresponding to each valence state and two or several phosphorus-containing flame retardants with different valence state in polyurethane are also introduced. Finally,the development trend is prospected by analyzing the existing problems.
Phosphorus-containing flame retardants with the advantages of high efficiency,no halogen and low toxicity are becoming one of the most important research branches in the field of flame retardant,which mainly focus on the research of synthesis and application of phosphorus-containing flame retardants. The phosphorus-containing flame retardants with different oxidation state of phosphorus have different flame retardant mechanism and different flame retardancy effect on polyurethane.The phosphorus-containing flame retardants are classified by the different oxidation state of phosphorus in four categories,which include red phosphorus( + 0),phosphite and hypophosphite( + 1),phosphonate( + 3) and phosphate( + 5). The feature and flame retardant mechanism are reviewed. Research progress on the application of the typical phosphorus-containing flame retardants corresponding to each valence state and two or several phosphorus-containing flame retardants with different valence state in polyurethane are also introduced. Finally,the development trend is prospected by analyzing the existing problems.
引文
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[16]熊联明,舒万艮,刘又年.微胶囊红磷阻燃剂在软质聚氨酯泡沫塑料中的应用研究[J].中国塑料,2004,18(6):72-76.
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[18]洪晓东,代文娟.含磷阻燃剂阻燃硬质聚氨酯泡沫塑料的性能研究[J].工程塑料应用,2013,41(8):95-99.
[19]朱靖,赵磊,吴勇.DOPO型含磷本质阻燃环氧树脂的研究进展[J].化工进展,2011,30(3):573-577.
[20]刘先龙,伍玉娇.覆铜板用反应型DOPO基有机磷系阻燃剂的研究进展[J].上海塑料,2014(3):12-20.
[21]KNIG A,KROKE E.Methyl-DOPO-a new flame retardant for flexible polyurethane foam[J].Polymers for Advanced Technologies,2011,22(1):5-13.
[22]张五一,王喜顺.新型DOPO基反应型阻燃剂在聚氨酯中的的应用[J].塑料,2013,42(4):82-84.
[23]LIU Y L,HE J Y,YANG R J.The thermal properties and flame retardancy of 9,10-Dihydro-9-oxa-10-phosphaphenanthrene10-oxide(DOPO)-Mg/Polyisocyanurate-Polyurethane foam composites[J].Bulletin of the Chemical Society of Japan,2016,89:779-785.
[24]LIU Y L,HE J Y,YANG R J.The preparation and properties of flame-retardant polyisocyanurate-polyurethane foams based on two DOPO derivatives[J].Journal of Fire Sciences,2016,34(5):431-444.
[25]CHEN X L,MA C Y,JIAO C M.Enhancement of flame-retardant performance of thermoplastic polyurethane with the incorporation of aluminum hypophosphite and iron-graphene[J].Polymer Degradation and Stability,2016,129:275-285.
[26]ZHAO B,HU Z,CHEN L,et al.A phosphorus-containing inorganic compound as an effective flame retardant for glass-fiber-reinforced polyamide 6[J].Journal of Applied Polymer Science,2011,119(4):2379-2385.
[27]杨旭峰,曹阳,职慧珍,等.次膦酸铝阻燃剂对硬质聚氨酯泡沫塑料阻燃改性的研究[J].中国阻燃,2013(4):7-9.
[28]LOREENZETTI A,BESCO S,HRELJA D,et al.Phosphinates and layered silicates in charring polymers:the flame retardancy action in polyurethane foams[J].Polymer Degradation and Stability,2013,98(11):2366-2374.
[29]YANG H Y,WANG X,SONG L,et al.Aluminum hypophosphite in combination with expandable graphite as a novel flame retardant system for rigid polyurethane foams[J].Polymers for Advanced Technologies,2014,25(9):1034-1043.
[30]MODESTI M,LORENZETTI A,BESCO S,et al.Synergism between flame retardant and modified layered silicate on thermal stability and fire behaviour of polyurethane nanocomposite foams[J].Polymer Degradation and Stability,2008,93(12):2166-2171.
[31]XU W Z,LIU L,WANG S Q,et al.Synergistic effect of expandable graphite and aluminum hypophosphite on flame-retardant properties of rigid polyurethane foam[J].Journal of Applied Polymer Science,2015,132(47):42842.
[32]RAMANI A,DAHOEA E.On flame retardancy in polycaprolactam composites by aluminium diethylphosphinate and melamine polyphosphate in conjunction with organically modified montmorillonite nanocaly[J].Polymer Degradation and Stability,2014,105:1-11.
[33]VAN DER VEEN I,DE BOER J.Phosphorus flame retardant:properties,production,environmental occurrence,toxicity and analysis[J].Chemosphere,2012,88(10):1119-1153.
[34]王靖宇,许博,邱勇,等.阻燃剂次膦(磷)酸盐的研究进展[J].塑料工业,2014,42(9):5-10.
[35]Zhao B,Chen L,Long J W,et al.Aluminum hypophosphite versus alkyl-substituted phosphinate in polyamide 6:flame retardance,thermal degradation,and pyrolysis behavior[J].Industrial&Engineering Chemistry Research,2013,52(8):2875-2886.
[36]SAMYN F,BOURBIGOT S.Thermal decomposition of flame retarded formulations PA6/aluminum phosphinate/melamine polyphosphate/organomodified clay:interactions between the constituents[J].Polymer Degradation and Stability,2012,97(11):2217-2230.
[37]CHEN X L,JIANG Y F,JIAO C M.Smoke suppression properties of ferrite yellow on flame retardant thermoplastic polyurethane based on ammonium polyphosphate[J].Journal of Hazardous Materials,2014,266:114-121.
[38]科莱恩金融(BVI)有限公司.烷基亚膦酸,烷基亚膦酸盐和烷基亚膦酸酯,它们的制备方法及它们的用途:中国,CN101720329A[P].2010-06-02.
[39]LORENZETTI A,MODESTI M,GALLO E,et al.Synthesis of phosphinated polyurethane foams with improved fire behavior[J].Polymer Degradation and Stability,2012,97(11):2364-2369.
[40]GAAN S,LIANG S,MISPREUVE H,et al.Flame retardant flexible polyurethane foams from novel DOPO-phosphonamidate additives[J].Polymer Degradation and Stability,2015,113:180-188.
[41]XI W,QIAN L J,CHEN Y J,et al.Addition flame-retardant behaviors of expandable graphite and[bis(2-hydroxyethyl)amino]-methylphosphonic acid dimethyl ester in rigid polyurethane foams[J].Polymer Degradation and Stability,2015,122:36-43.
[42]XI W,QIAN L J,HUANG Z G,et al.Continuous flame-retardant actions of two phosphate esters with expandable graphite in rigid polyurethane foams[J].Polymer Degradation and Stability,2016,130:97-102.
[43]YUAN Y,YANG H Y,YU B,et al.Phosphorus and nitrogencontaining polyols:synergistic effect on the thermal property and flame retardancy of rigid polyurethane foam composites[J].Industrial&Engineering Chemistry Research,2016,55(41):10813-10822.
[44]CHEN M J,XU Y J,RAO W H,et al.Influence of valence and structure of phosphorus-containing melamine salts on the decomposition and fire behaviors of flexible polyurethane foams[J].Industrial&Engineering Chemistry Research,2014,53(21):8773-8783.
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