含长脂肪链木质素协同聚磷酸铵对聚乳酸阻燃性能及力学性能的影响

Effect of Lignin with Long Aliphatic Chain Combined with Polyammonium Phosphate on the Flame Retardant and Mechanical Properties of Intumescent Flame Retardant Polylactic Acid

  • 摘要: 聚乳酸(PLA)作为生物基可降解材料,被广泛用于诸多领域。但PLA因自身的结构组成特点易燃,限制了其在电子、电器、汽车等领域的实际应用。因此有必要对PLA进行阻燃改性研究。以木质素作为主要原料,十二烷基三甲氧基硅烷为改性剂,通过一步法在碱木质素中引入长脂肪链和硅元素,制备了含长脂肪链木质素(RLig)。热失重分析表明RLig在空气条件下具有较强的成炭能力,550℃时的残炭量较改性前木质素的2.3%提升至27.8%。将RLig与聚磷酸铵(APP)复配用于制备阻燃聚乳酸复合材料(RLig-APP/PLA),并对材料的阻燃性能、燃烧行为、力学性能等进行了研究。结果表明,当APP与RLig的质量比为4∶1时,10wt%的总添加量可使PLA(2RLig-8APP/PLA)达到难燃级别,垂直燃烧通过V-0级,而同等条件下 2Lig-8APP/PLA 的 LOI 值为 26%,UL-94 仅为 V-2 级别。锥形量热测试结果分析发现,2RLig-8APP/PLA的热释放速率峰值(pHRR)显著降低,火灾安全性明显提高。凝聚相与气相产物分析表明,RLig的引入使得阻燃PLA的阻燃机理以气相阻燃为主,凝聚相阻燃为辅。此外,2RLig-8APP/PLA的力学性能得到了明显改善,拉伸强度达到58.3 MPa,冲击强度为9.6 kJ·m−2,较2Lig-8APP/PLA提高了一倍多。同时,2RLig-8APP/PLA的储能模量也有所提高。

     

    Abstract: Polylactic acid (PLA), as a biodegradable material based on biomass, is widely used in many fields. However, due to its own structural and compositional characteristics, PLA is flammable, which limits its practical application in electronics, electrical appliances, automobiles and other fields. Therefore, it is necessary to conduct flame retardant modification research on PLA. Using lignin as the main raw material and dodecyltrimethoxysilane as the modifier, long aliphatic chains and silicon element were introduced into alkali lignin through a one-step process, and the lignin with long aliphatic chains (RLig) was prepared. Thermogravimetric analysis showed that RLig had good charring ability under air condition, and the residual char content at 550℃ increased from 2.3% of the unmodified lignin to 27.8%. RLig was compounded with ammonium polyphosphate (APP) to prepare flame retardant polylactic acid composite materials (RLig-APP/PLA), and the flame retardant properties, combustion behavior, and mechanical properties were researched. The results indicated that when the mass ratio of APP to RLig was 4∶1, a total addition of 10wt% made 2RLig-8APP/PLA have the limiting oxygen index(LOI) value of 27%, and pass the vertical combustion UL-94 V-0 grade. While the LOI value of 2Lig-8APP/PLA with unmodified Lig was 26% and the vertical burning UL-94 only passed V-2 rating. Meanwhile, the analytic results of the cone calorimeter test showed that the peak heat release rate (pHRR) of 2RLig-8APP/PLA was significantly reduced, and the fire safety was greatly improved. The analysis of condensed and gas phase products showed that the introduction of RLig made the flame retardant mechanism of flame retardant PLA dominated by gas phase flame retardant, supplemented by condensed phase flame retardant. In addition, the mechanical properties of 2RLig-8APP/PLA were significantly improved, with a tensile strength of 58.3 MPa and an impact strength of 9.6 kJ·m−2, more than doubled compared to 2Lig-8APP/PLA. At the same time, the storage modulus of 2RLig-8APP/PLA were also improved.

     

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