Li Jianxing, Yan Zepei, Liu Ming, Han Xiaokun, Lu Tianyun, Liu Ruiyin, Zhao Shugao, Lv Qing, Li Bo, Zhao Shengqin, Wang He
Key Laboratory of Rubber-Plastics of Ministry of Education/Shandong Provincial Key Laboratory of Rubber-Plastics, School of Polymer Science and Engineering, Qingdao University of Science & Technology, Qingdao 266042, China.
Jiangyin Haida Rubber and Plastic Co., Ltd., Jiangyin 214424, China.
ACS Omega. 2023 Jun 5;8(24):21549-21558. doi: 10.1021/acsomega.3c00714. eCollection 2023 Jun 20.
In this study, we present an innovative environmental silicon-, phosphorus-, and nitrogen-triple lignin-based flame retardant (Lig-K-DOPO). Lig-K-DOPO was successfully prepared by condensation of lignin with flame retardant intermediate DOPO-KH550 synthesized via Atherton-Todd reaction between 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and γ-aminopropyl triethoxysilane (KH550A). The presence of silicon, phosphate, and nitrogen groups was characterized by FTIR, XPS, and P NMR spectroscopy. Lig-K-DOPO exhibited advanced thermal stability compared with pristine lignin supported by TGA analysis. The curing characteristic measurement showed that addition of Lig-K-DOPO promoted the curing rate and crosslink density to styrene butadiene rubber (SBR). Moreover, the cone calorimetry results indicated Lig-K-DOPO conferred impressive flame retardancy and smoke suppression. The addition of 20 phr Lig-K-DOPO reduced SBR blends 19.1% peak heat release rate (PHRR), 13.2% total heat release (THR), 53.2% smoke production rate (SPR), and 45.7% peak smoke production rate (PSPR). This strategy provides insights into multifunctional additives and greatly extends the comprehensive utilization of industrial lignin.
在本研究中，我们展示了一种创新的基于环境硅、磷和氮的三官能团木质素基阻燃剂（Lig-K-DOPO）。Lig-K-DOPO是通过木质素与阻燃中间体DOPO-KH550缩合成功制备的，该中间体是通过9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）与γ-氨丙基三乙氧基硅烷（KH550A）之间的Atherton-Todd反应合成的。通过傅里叶变换红外光谱（FTIR）、X射线光电子能谱（XPS）和磷核磁共振光谱（P NMR）对硅、磷酸盐和氮基团的存在进行了表征。热重分析（TGA）表明，与原始木质素相比，Lig-K-DOPO具有更高的热稳定性。固化特性测量表明，添加Lig-K-DOPO可提高丁苯橡胶（SBR）的固化速率和交联密度。此外，锥形量热法结果表明，Lig-K-DOPO具有令人印象深刻的阻燃性和抑烟性。添加20份Lig-K-DOPO可使SBR共混物的峰值热释放速率（PHRR）降低19.1%，总热释放（THR）降低13.2%，产烟速率（SPR）降低53.2%，峰值产烟速率（PSPR）降低45.7%。该策略为多功能添加剂提供了见解，并极大地扩展了工业木质素的综合利用。
