协效阻燃型松香基聚氨酯硬泡结构设计及其构效关系研究

Polyurethane foam (PUF) has been widely used as insulation materials in many fields for good physical properties.However,it easily flammable and emit a large amount of smoke while burning. So,the flame retardant is an important requirement of PUF when they are used in buildings. In recent years,reasearch on flame retardant of PUF is a newly emerged area and no encouraging result has been obtained yet. The purpose of this proposal is to develop a highly flame retardant PUF product from rosin, a readily available and renewable natural resource. Our approach is to introduce highly flame retardant aromatic hetercyclic ring and phosphorus nitrogen elements into rosin. PUF will be developed from this modified rosin based polyol. The four main objectives of this proposed reseach are 1) investigate the thermal stability and combustion property of resulting rosin based PUF; 2) analyze the chemical structure and composition of the combustion product from the rosin based PUF; 3) investigate the synergetic effects of aromatic heterocyclic ring structure and phosphorus-nitrogen elements on the flame retardant properties of rosin based PUF, such as maximum heat release rate and total heat release and mass loss rate; and 4) figure out the structure-activity relationship between rosin based polyol and rigid PUF flame retardant properties,meanwhile explore the flame retardant mechanism.It is excepted that the successful completion of this project will provide a key technology for the development of high value-added products from rosin as well as theoretical knowledge in the study of synergetic flame retardant.

针对目前聚氨酯泡沫塑料易燃烧、燃烧发烟量大等缺点，本项目设想将酚醛泡沫塑料的高难燃性能优点与协效阻燃技术相结合，充分利用松香分子结构独特、产量大等特点，在松香三元菲环骨架上引入阻燃芳杂环及磷氮阻燃元素，设计合成松香基芳杂环磷氮多元醇；并制备松香基阻燃型聚氨酯硬泡；通过对所得材料的热稳定性和燃烧性能研究，结合燃烧后产物的结构和成分分析，对比不同分子结构的多元醇阻燃聚氨酯时各项性能的差异，考察阻燃元素在最大热释放速率、总热释放量以及质量损失率等方面的协效关系；重点研究多元醇结构和聚氨酯硬泡阻燃性能的构效关系，探索阻燃机理。本项目可解决我国松香深加工利用率低的关键技术问题，同时为高分子材料的协效阻燃研究提供理论基础。

针对目前我国松香产品附加值低以及生物质基聚氨酯硬泡易燃烧、燃烧发烟量大等特点。本项目利用松香分子独特结构，在松香三元菲环骨架上引入阻燃刚性环及磷氮阻燃元素，制备松香基阻燃多元醇和聚氨酯硬泡；主要研究内容如下：. （1）完成了松香基协效阻燃多元醇的合成及和结构表征工作。分别研究了3种改性松香树脂酸的合成和结构鉴定；同时探索了阻燃元素磷、氮、酚醛结构的引入对多元醇的羟值、黏度等性能的影响，发现酚醛结构引入量越多，多元醇的粘度越大，热稳定性越高，羟值越低；最终确定了较优的引入量和比例，获得了5种松香基阻燃多元醇。（2）考察了多元醇在反应过程中的聚合反应行为及活性差异，并确定了多元醇结构和性能对聚氨酯硬泡制备配方的影响；结果表明，不同松香基阻燃多元醇的发泡活性较普通苯酐聚酯多元醇高，不同阻燃基团含量的多元醇活性相差不大；泡沫相对压缩强度增加，泡孔导热系数也较小。(3)研究了阻燃型松香基多元醇对聚氨酯硬泡的阻燃效果及不同阻燃元素之间的协同效应；考察了阻燃元素在最大热释放速率、总热释放量以及质量损失率等方面的协效关系；明确了阻燃机理。成功开发出适合不同用途的阻燃型松香基聚氨酯泡沫材料，能够满足国家标准8624-2012 B1要求。本项目发表相关论文7篇，其中SCI 收录4篇，EI收录1篇，中文核心2篇；申请国家发明专利4项，获授权2项；培养研究生2名；2014年8月参加全国聚氨酯工业协会年会并做分会场报告，相关论文“结构阻燃型生物质基硬质聚氨酯泡沫制备及性能研究”获得2014年度中国聚氨酯工业协会年会论文一等奖。. 本项目的完成解决了目前以松香为原料制备的聚氨酯硬泡阻燃性低的问题，为松香高附加值的大规模应用提供一种可行的途径，对我国建筑物节能措施的实施、生态环境的改善及农民收入的增加将起到十分积极的促进作用。