六氨基环三磷腈盐的合成及其阻燃抑烟作用研究

Phosphazenes are considered to be the second generation of phosphorus-nitrogen containing intumescent flame retardants with great development potential.However,these retardants have been not realized the industrialization production and application because the existing products reported have some shortcomings such as synthesis of high difficulty,expensive price,large waste emissions or poor balanced properties.In order to address the above deficiencies,in this item,novel phosphazenes-hexaamidocyclotriphosphazene salts with high phosphorus and nitrogen contents,for example,hexaamidocyclotriphosphazene polyphosphate and hexaamidocyclotriphosphazene cyanurate,haxaamidocyclotri-.phosphazene borate,etc,are designed by according the synthetic principles of phosphazene and flame retardancy and smoke-suppression theory as well as simulating the stuctur of green fire retardant-melamine salts,which can be prepared by simple and environmental friendly neutrailization or metathesis reactions of haxaamidocyclotriphosphazene with bargain acids or soluble salts(for example cyanuric acid,polyphosphoric acid,sodium borate,etc)in about 100% of the yield，and from which several green flame retardants with good thermal stability,excellent flame retardancy and smoke-suppression and cheap price would be screened out by further investigating their thermal behavior characteristics,fire retardancy and smoke-suppresion. Their fire retardant and smoke-suppression mechanisms will be also studied by identifying the composition and chemical structure of thermal decomposition evolved products and combustion residues as well as theoretical analysis,which will provide theoretical guidance for the proper use and development of novel flame retardants.

磷腈被认为是极具发展潜力的第二代绿色磷-氮系膨胀型阻燃剂,但由于已报道的磷腈类阻燃剂的合成难度高、价格昂贵或综合性能不佳等缺点而使其一直未实现工业化生产和应用。为此，本课题根据阻燃抑烟理论和磷腈的合成原理，并模仿三聚氰胺盐的结构，设计了一类磷氮含量高的新型磷腈化合物-六氨基环三磷腈盐，如聚磷酸六氨基环三磷腈、六氨基环三磷腈氰尿酸盐、六氨基环三磷腈硼酸盐等。它们由六氨基磷腈与各种廉价的酸或可溶性盐（如氰尿酸、多磷酸、硼酸钠等）通过中和或复分解反应制得，合成过程十分简单和环境友好，产率接近100%。通过进一步研究它们的热行为特征和阻燃及抑烟作用，将从中筛选出几种热稳定性好、阻燃抑烟效率高、价格较便宜的绿色阻燃剂。通过鉴定热分解挥发产物和燃烧残余物的化学结构及组成，并结合理论分析，研究它们的阻燃及抑烟作用机理，以便为今后正确使用和研究新型阻燃剂提供理论指导。

磷腈被认为是极具发展潜力的第二代绿色磷-氮系膨胀型阻燃剂,但由于已报道的磷腈类阻燃剂合成难度高、价格昂贵或综合性能不佳等缺点而使其一直未实现工业应用。为此，本项目设计和合成了系列六氨基环三磷腈衍生物阻燃剂，研究了它们的热稳定性、阻燃作用及作用机理。结果表明：开发出的三聚氰胺改性聚氨基环三磷腈、苯氧基改性聚氨基环三磷腈和苯基改性聚氨基环三磷腈等三种新型阻燃剂及聚氨基环三磷对环氧树脂固化物具有良好的阻燃作用，且热稳定性良好；由聚氨基环三磷腈和三（2-羟乙基）异氰尿酸酯复合而成的膨胀型阻燃剂对聚乙烯和聚丙烯具有良好的阻燃作用；六氨基环三磷腈及六（N-羟甲基）氨基环三磷腈对纸具有良好的阻燃作用，并且用六氨基环三磷腈及六（N-羟甲基）氨基环三磷腈和部分甲醚化三聚氰胺甲醛树脂的复合物制得的阻燃纸具有良好的耐水性和强度；磷腈阻燃剂主要是通过凝聚相机理产生阻燃作用。阻燃剂在高温下生成磷酸类化合物，磷酸类化合物具有强脱水作用，能促进聚合物炭化，同时聚合物等分解生成的惰性气体使炭层发泡，形成膨胀性炭层。这种致密的膨胀性炭层通过隔热、隔氧及抑制聚合物进一步分解而产生阻燃作用；阻燃剂的阻燃作用不仅与其阻燃元素（P、N）的含量有关，而且与阻燃剂的化学结构有关。化学结构的少许变化对其阻燃作用会有很大影响。本研究还改进了六氯环三磷腈、六氨基环三磷腈、聚氨基环三磷腈、六苯氧基环三磷腈和六苯胺基环三磷腈的合成工艺。以上成果将对今后开发高效阻燃剂具有重要的指导作用，对六氯环三磷腈、六苯氧基环三磷腈、六苯胺基环三磷腈和高性能阻燃纸等的产业化具有重要的实用价值。