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一种具有优异淬灭和炭化能力的双羟基双二苯基膦氧化物化合物用于木质素基环氧树脂的制备

Fabrication of a bi-hydroxyl-bi-DOPO compound with excellent quenching and charring capacities for lignin-based epoxy resin.

作者信息

Lu Xinyu, Gu Xiaoli

机构信息

Co-Innovation Center for Efficient Processing and Utilization of Forest Products, College of Chemical Engineering, Nanjing Forestry University, 159 Longpan Road, Nanjing 210037, PR China.

Co-Innovation Center for Efficient Processing and Utilization of Forest Products, College of Chemical Engineering, Nanjing Forestry University, 159 Longpan Road, Nanjing 210037, PR China.

出版信息

Int J Biol Macromol. 2022 Apr 30;205:539-552. doi: 10.1016/j.ijbiomac.2022.02.103. Epub 2022 Feb 22.

Abstract

In this study, lignin-based epoxy resins (EP) were fabricated using lignin, phenol and glyoxal as crosslinking reagents. For improving the flame retardancy, a bi-DOPO compound with bi-hydroxyl structure was successfully synthesized, containing excellent quenching and charring capacities. Good pyrolysis behaviors of as-synthesized flame retardant resulted in significant quenching effect via structure decomposition to release PO and PO free radicals for capturing reactive H and OH radicals produced from epoxy combustion. With addition of 0.18 wt% phosphorus, epoxy composite (10% LPG-ER-4) passed V-0 rating with high limited oxygen index (LOI) value of 35.2%. Cone calorimeter tests showed that heat release (including heat release rate (HRR) and total heat release (THR)) from combustion was reduced with assistance of flame retardant. Char residue analyses illustrated that bi-hydroxyl structure in DOPO-based flame retardant benefited the formation of char layer with higher compactness and integrity to serve as a protective shell of interior epoxy matrix. Furthermore, exterior pore size of char residue was narrowed or blocked to avoid the release of heat and volatiles generated from combustion. This study provided a feasible method to improve flame retardancy of lignin-based EP and proposed flame-retardant mechanism both in gaseous and solid phases.

摘要

在本研究中,以木质素、苯酚和乙二醛作为交联剂制备了木质素基环氧树脂(EP)。为提高阻燃性,成功合成了一种具有双羟基结构的双二苯基氧化膦(bi-DOPO)化合物,其具有优异的淬灭和炭化能力。所合成阻燃剂良好的热解行为通过结构分解产生PO和PO自由基,捕获环氧树脂燃烧产生的活性H和OH自由基,从而产生显著的淬灭效果。添加0.18 wt%的磷后,环氧复合材料(10% LPG-ER-4)通过了V-0等级,极限氧指数(LOI)高达35.2%。锥形量热仪测试表明,在阻燃剂作用下,燃烧热释放(包括热释放速率(HRR)和总热释放(THR))降低。残炭分析表明,基于DOPO的阻燃剂中的双羟基结构有利于形成致密性和完整性更高的炭层,作为内部环氧基体的保护壳。此外,残炭的外部孔径变窄或堵塞,以避免燃烧产生的热量和挥发性物质释放。本研究提供了一种提高木质素基EP阻燃性的可行方法,并提出了气相和固相的阻燃机理。

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