负载金属柱撑蒙脱土对阻燃硬质聚氨酯泡沫的抑烟减毒作用及机理研究

To solve the problem that the great volumes of smoke and toxic gases such as CO and HCN produce during the burning of flame retarded rigid polyurethane foam (FRRPUF), a novel metal-supported pillared montmorillonite (PILM) is designed and synthesized in this proposal, which plays a role of catalytic effect on char-forming, smoke suppression and toxic gases reduction during burning of FRRPUF. A novel PILM is synthesized by cation exchange and hydrogen bonds effect, and the factors effect on the morphology of PILM are studied, which aims to regulate the composition and structure of PILM. The effects of PILM on char-forming, smoke production and toxic gases production of FRRPUF are investigated; moreover, the relationship between the composition and structure of PILM and its catalytic properties is explored. The effects of PILM on thermal decomposition products in gas phase and condensed phase, thermal decomposition process, and char-forming behavior of FRRPUF are investigated by online analytical technology such as TG-FTIR-GC-MS, PyGC-MS and RT-FTIR; thus, the smoke suppression and toxicity reduction mechanism of PILM in FRRPUF could be revealed by the above study. The novel PILM with excellent smoke suppression and toxicity reduction, and the corresponding mechanism will be obtained based on this project. Furthermore, a novel proposal is developed to design and prepare flame retarded materials with low smoke and low toxicity.

针对阻燃硬质聚氨酯泡沫（FRRPUF）在燃烧时会产生大量浓烟、CO和HCN等剧毒气体这一难题，本项目旨在通过设计合成新型负载金属柱撑蒙脱土（PILM），使其在FRRPUF燃烧时兼具催化成炭及催化剧毒气体向低毒物质转化的功能。研究PILM对FRRPUF的成炭率、烟气及HCN等剧毒气体生成量的影响规律，构筑PILM组成及结构与其催化性能的内在关系。通过离子交换和氢键作用合成新型PILM，考察影响目标产物形态的因素，以达到PILM结构与组成可调控之目的。采用TG-FTIR-GC-MS、PyGC-MS、RT-FTIR等在线分析技术，通过分析PILM对FRRPUF热解气相和凝聚相产物组成、热解历程和成炭行为的影响，研究PILM在气相和凝聚相的作用机制并揭示其抑烟减毒机理。通过研究，本项目预期获得对FRRPUF有优异抑烟减毒效果的PILM及其作用机理，为低烟低毒阻燃高分子材料的设计与开发提供理论依据。

硬质聚氨酯泡沫材料包括阻燃硬质聚氨酯泡沫材料（FRPU）燃烧时会产生大量浓烟和CO及HCN等有毒气体，已限制了其进一步应用。本项目针对这一问题，首先深入研究FRPU的组成（异氰酸酯指数、聚醚多元醇与聚酯多元醇比例、阻燃剂类型及添加量）对其燃烧行为及燃烧烟气中毒性气体浓度的影响规律；接着，设计制备系列负载金属柱撑蒙脱土（PILM），并应用于FRPU中；最后，综合利用多种技术手段研究了PILM在FRPU中的抑烟减毒作用及机理。研究结果表明：硬质聚氨酯泡沫材料自身的组成对其燃烧行为及燃烧烟气的影响不大；磷酸三（2-氯丙基）酯（TCPP）、甲基磷酸二甲酯（DMMP）、聚磷酸铵（APP）、三聚氰胺磷酸盐（MP）、三聚氰胺聚磷酸盐（MPP）和阻燃多元醇均会显著增大FRPU燃烧烟气中有毒气体的生成量；PILM在TCPP、DMMP和MPP阻燃硬质聚氨酯泡沫体系中表现出一定的抑烟减毒作用，在阻燃多元醇阻燃硬质聚氨酯泡沫体系表现出更加的抑烟减毒作用；负载双金属PILM的抑烟减毒作用明显大于负载单金属的PILM，其中负载Ti和La及Zr和La的PILM的抑烟减毒作用最为突出。热解行为和烟气分析数据表明，PILM通过以下途径实现抑烟减毒：（1）蒙脱土的阻隔作用，降低了烟气生成量；（2）负载金属的催化作用，降低有毒气体（HCN和CO等）和有毒烟气前驱体（如含异氰酸酯基团的热解产物和苯胺等）的生成量。以上研究对于阻燃材料的抑烟减毒及机理的研究具有重要的科学意义，对于低烟低毒阻燃硬质聚氨酯泡沫材料的研发具有较强的指导作用。