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磷氮共聚阻燃剂的合成及其在聚丙烯中的应用。

Synthesis and Flame Retardant Behavior of Phosphorous- and Nitrogen-Containing Copolymer and Its Application in Polypropylene.

机构信息

State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024, China.

SINOPEC (Beijing) Research Institute of Chemical Industry Co., Ltd, Beijing, 100013, China.

出版信息

Macromol Rapid Commun. 2024 Oct;45(20):e2400376. doi: 10.1002/marc.202400376. Epub 2024 Jul 15.

DOI:10.1002/marc.202400376
PMID:39008820
Abstract

In this study, a 4-(hydroxymethyl)-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide (PEPA)-functionalized acrylate monomer, PEPAA, is designed and utilized for the synthesis of macromolecular flame retardants poly(PEPAA-co-AM) with varying PEPAA/AM ratio through copolymerization with acrylamide (AM). The poly(PEPAA-co-AM) is then incorporated into polypropylene (PP) to prepare PP/poly(PEPAA-co-AM) composites. The flame retardant effect of poly(PEPAA-co-AM) on PP is investigated using cone calorimetric test (CCT), and compared with that of PEPAA homopolymer (P-PEPAA), AM homopolymer (PAM), and blends of P-PEPAA/PAM. The results demonstrate that, in comparison with P-PEPAA, PAM, and blends of P-PEPAA/PAM, the incorporation of poly(PEPAA-co-AM) significantly enhances the flame retardancy of PP. Notably, the best flame retardancy is achieved when the ratio of PEPAA/AM copolymerization in poly(PEPAA-co-AM) is 2/8. The morphology and composition of residual chars from combustion are analyzed using SEM-EDS while the residual graphitization degree is examined through Raman spectroscopy. Additionally, TG-FTIR-MS is utilized to investigate the pyrolysis products in gas phase during thermal decomposition of poly(PEPAA-co-AM). Based on these experimental results, a flame retardant mechanism for poly(PEPAA-co-AM) is proposed. The PP/poly(PEPAA-co-AM) composites not only retain the excellent processing properties of pure PP but also exhibit enhanced mechanical properties.

摘要

在这项研究中,设计并利用了一种 4-(羟甲基)-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷 1-氧化物(PEPA)功能化的丙烯酸盐单体 PEPAA,通过与丙烯酰胺(AM)共聚合成了具有不同 PEPAA/AM 比的高分子量阻燃剂聚(PEPAA-co-AM)。然后将聚(PEPAA-co-AM)掺入聚丙烯(PP)中,制备 PP/聚(PEPAA-co-AM)复合材料。通过锥形量热试验(CCT)研究了聚(PEPAA-co-AM)对 PP 的阻燃效果,并与 PEPAA 均聚物(P-PEPAA)、AM 均聚物(PAM)和 P-PEPAA/PAM 混合物进行了比较。结果表明,与 P-PEPAA、PAM 和 P-PEPAA/PAM 混合物相比,聚(PEPAA-co-AM)的掺入显著提高了 PP 的阻燃性能。值得注意的是,当聚(PEPAA-co-AM)中 PEPAA/AM 共聚的比例为 2/8 时,阻燃效果最佳。通过扫描电子显微镜-能谱分析(SEM-EDS)分析了燃烧残余炭的形貌和组成,通过拉曼光谱检查了残余炭的石墨化程度。此外,通过 TG-FTIR-MS 研究了聚(PEPAA-co-AM)热分解过程中气相中的热解产物。基于这些实验结果,提出了聚(PEPAA-co-AM)的阻燃机理。PP/聚(PEPAA-co-AM)复合材料不仅保留了纯 PP 的优异加工性能,而且还表现出增强的机械性能。

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