一种新型高效含多磷氧化态阻燃剂在环氧树脂中的应用  

Application of a novel highly effective flame retardant with multi phosphorous oxidation states in epoxy resins

作　　者：张李鹏 王晓明 杜宝帅 Zhang Lipeng;Wang Xiaoming;Du Baoshuai(State Grid Shandong Electric Power Research Institute,Jinan Shandong 250002,China;Shandong Smart Grid Technology Innovation Center,Jinan Shandong 250002,China)

机构地区：[1]国网山东省电力公司电力科学研究院,山东济南250002 [2]山东省智能电网技术创新中心,山东济南250002

出　　处：《消防科学与技术》2025年第3期408-416,共9页Fire Science and Technology

基　　金：国网山东省电力公司科技项目资助“变电站火灾场景下高力学性能防火涂料研究与开发”(520626230020)。

摘　　要：为开发环氧树脂(EP)用高效无卤阻燃剂,以对羟基苯甲醛、三氯氧磷和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)为原料,制备了一种新型阻燃剂DOPPO,其分子结构含有两种磷氧化态以及羟基。研究了DOPPO对EP复合材料的热性能、阻燃性能以及耐火性能的影响。测试结果表明,有机磷阻燃剂的分子结构影响EP复合材料的阻燃性能和耐火性能。相比9,10-二氢-9-氧杂-10-磷杂菲-10-基-(4-羟基苄醇)(DOPh)和磷酸三苯酯(TPP),DOPPO具有明显的协同阻燃效应,在EP中表现出更高效的阻燃性能和耐火性能。其中,当磷元素质量分数仅为0.42%时,EP/DOPPO在UL 94垂直燃烧测试中达到V-0级,获得了较高的LOI值,34.6%,形成的更致密的膨胀残炭层能抑制热量和有毒烟气的释放。TG-IR分析结果表明,有含磷挥发物的生成,这可能为DOPPO提供了对EP的气相阻燃功能。DOPPO较好的阻燃性能可能归因于气相中磷杂菲基团的淬灭效应和凝聚相中磷酸酯基团和磷杂菲基团与羟基共同作用的成炭效应。此外,大板燃烧试验结果显示,DOPPO在防火涂层的膨胀倍率以及耐火性能上优于DOPh和TPP。In order to develop highly efficient halogen-free flame retardants of epoxy resins(EP),a novel flame retardant DOPPO,which contains two phosphorus oxidation states and hydroxyl groups,was synthesized from p-Hydroxybenzaldehyde,phosphorus oxychloride,and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO).The influence of DOPPO on the thermal,flame-retardant,and fire-resistant performance of EP composites was studied.Tests showed that the flame retardance and fire resistance of EP composites are influenced by the molecular structure of organic phosphorus-containing flame retardant.Compared with DOPh and TPP,DOPPO shows obvious synergistic flame retardant effect,and the most efficient flame retardance and fire resistance in EP.In detail,when the phosphorus content in EP is low at only 0.42%,the EP/DOPPO acquired the UL 94 V-0 rating and obtained a higher LOI value of 34.6%,the formation of more compact expanded char residues can inhibit the release of heat and toxic smoke.TG-IR analysis shows the generation of phosphorus containing volatiles,which may provide DOPPO with gas phase flame retardant function for EP.The better flame retardant performance of DOPPO is ascribed to the quenching effect of the phosphaphenanthrene group in the gas phase and the charring effect of phosphate ester group and phosphaphenanthrene group with hydroxyl group in the condensed phase.And,the results from the large-plate combustion test reveals that DOPPO was superior to DOPh and TPP in terms of expansion ratio as well as fire-resistant performance of the fireproof coatings.

关 键 词：环氧树脂 阻燃剂 多磷氧化态 阻燃性能 耐火性能 

分 类 号：X932[环境科学与工程—安全科学] TU545[建筑科学—建筑技术科学]