新型含P—C键多异氰酸酯的合成及相应聚氨酯阻燃性能

Polyurethane (PU) is a class of versatile organic polymer materials. Because of its product form diversity, easy molding process, special durability, good hydrolysis stability, and excellent wear resistance, PU has been widely used in many fields such as construction, transportation and electronic electrician. However, its flammability nature restricts its applications; therefore, it is important to improve flame retardancy of PU. To solve this problem, effective flame retardants are used to retard the burning of polyurethane. Through the use of phosphorous-containing reactive-flame retardant, PU materials containing phosphorus chemically bonded to the polymer chain have the advantages of permanent attachment and perfect homogeneous distribution, and requires smaller amounts of flame retardant agent. Consequently, this way of phosphorus incorporation in the material should have a much smaller influence upon the physical and mechanical properties of the polymer. They have also several advantages such as low toxicity and corrosivity, as well as producing low smoke during burning. In this project we propose to design and synthesize three novel containing P—C bonds polyisocyanates from tetrakis(hydroxymethyl) phosphonium sulfate (THPS), and use them as reactive-flame retardants for the preparation of flame-retardant polyurethane. Systematic study the flame-retardant property of the responding PU, and discuss the flame-retardant mechanism of containing P—C bonds polyisocyanates, we hope to clarify the intrinsic relationships between structure of flame-retardant and performance of polyurethane, and to explore the new way which can not only improve the flame-retardant property but also have a much smaller influence upon other properties.

聚氨酯(PU)是一种多功能有机高分子材料，由于其产品形态多样性、简便的成型工艺、特殊的耐用性、良好的水解稳定性和优良的耐磨性而被广泛用于建筑、交通运输和电子电工等领域。而聚氨酯树脂的易燃性极大的限制了材料的使用范围,因此提高聚氨酯的阻燃性具有重要意义，使用有效的阻燃剂可以解决这一问题。使用反应型含磷阻燃剂使磷原子化学键合到聚合物链中的聚氨酯材料具有持久不溢出、完全均匀分布和使用阻燃剂的量少等优点；且磷原子的引入对材料的物理和机械性能影响较小；同时还具有低毒低腐蚀性，燃烧过程中少烟等优点。本项目以四羟甲基硫酸鏻（THPS）为原料，拟设计并合成三种新型含P—C键的多异氰酸酯，并将其作为反应型阻燃剂用于制备阻燃的聚氨酯树脂。在系统研究相应聚氨酯的阻燃性能、热稳定性和力学性能，并探讨含P—C键多异氰酸酯的阻燃机理基础上，力求阐明阻燃剂结构与聚氨酯性能的内在关系，探索提高材料阻燃性能同时降低对其他性能的影响。

“精细化、专用化和绿色化”已经成为磷化工发展的主旋律。在高分子中引入少量的磷可以显著改善材料的阻燃性、金属黏结性等。因此，将磷引入高分子中以获得性能优异的材料是将初级磷化学品精细化的有效途径之一。本研究拟以磷化工尾气PH3的衍生物四羟甲基硫酸鏻(THPS)为原料制备三种含P—C键的多元异氰酸酯，并将其作为反应型含磷阻燃剂将磷元素化学键合到聚氨酯材料中，以提高材料的阻燃性且降低对其他性能的影响。项目的主要研究内容及结果包含五个方面：（1）以THPS为原料成功地合成并表征了三种含磷的多元氨基甲酸甲酯，即Carbamate-Trimer、Carbamate-Dimer和Carbamate-Tetrakismer，它们可作催化热裂解法制备含P—C键多元异氰酸酯的原料。以Carbamate-Trimer、Carbamate-Dimer为原料制备并表征了两种含P—C键的多元胺，即三胺甲基氧化磷（NH2-Trimer）和二氨甲基苄基氧化磷（NH2-Dimer），以用作固体光气法制备含P—C键的多元异氰酸酯的原料。（2）探究了纳米ZnO、Zn粉、金丝和蒙脱土等四种催化剂，发现纳米ZnO能显著降低热裂解温度是催化热裂解法的适宜催化剂。并分别将Carbamate-Trimer和Carbamate-Dimer与不同的多元醇（聚乙二醇500、聚乙二醇800、聚丙二醇500、聚丙二醇800等）直接在纳米ZnO催化剂作用下制备出几种不同含P—C键聚氨酯材料，对其结构进行表征，并研究了材料的热稳定性及其阻燃性。（3）分别以NH2-Trimer和NH2-Dimer为原料制备并表征了两种含磷苯并噁嗪，研究其固化动力学，并研究了相应树脂对重金属离子的吸附性能。并以中间产物含磷希夫碱为配体制备多种金属配合物，对其结构进了表征，研究了各种金属配合物的性能。（4）以NH2-Dimer和1,3,5-苯三甲酸为原料建立A2+B3体系制备含磷半芳型超支化聚酰胺，对其结构进行表征，并研究了材料的性能。（5）对聚磷酸铵/氢氧化铝/云母/硅橡胶复合材料的阻燃性能及协同效应进行了研究，以此探讨了含磷阻燃剂在高分子材料中的阻燃机理。