Peng Wei, Xu Yu-Xuan, Nie Shi-Bin, Yang Wei
School of Safety Science and Engineering, Anhui University of Science and Technology Huainan 232001 P. R. China
RSC Adv. 2021 Sep 17;11(49):30943-30954. doi: 10.1039/d1ra05709j. eCollection 2021 Sep 14.
Phosphorus-containing flame retardants have received huge interest for improving the flame retardant behavior of epoxy resins (EP) over the past few decades. However, a satisfactory flame retardant effect requires high loading of most phosphorus-containing flame retardants, resulting in the deterioration of the thermo-mechanical properties of the flame retardant epoxy materials. To obtain the flame retardant EP with excellent comprehensive properties, a furfurylamine-derived bis-DOPO derivative (FA-bis-DOPO) was synthesized from bio-mass as a co-curing agent for the flame retardant EP. The incorporation of FA-bis-DOPO improved the mechanical strength, the storage modulus and the glass transition temperature of the flame retardant epoxy materials, owing to its stiffness and reactivity with the epoxy matrix to enhance the crosslinking density. The EP material containing 5.0 wt% of FA-bis-DOPO had an LOI of 31.0% and UL-94 V-0 rating, while the pristine EP had an LOI of 23.5% and failed in the UL-94 test, manifesting the high flame retardant efficiency of FA-bis-DOPO. Besides, the cone calorimeter results demonstrated that the PHRR, THR, and TSP values of the EP/FA-bis-DOPO-5.0 were 28.0%, 27.3%, and 9.9% lower than those of the pristine EP, respectively. The flame retardant mechanism of FA-bis-DOPO could be attributed to the combined vapor and condensed phase mechanisms which involved the interruption of the combustion chain reaction by quenching radicals and the inhibition of the transfer of pyrolytic volatile products by catalytic formation of an intact and compact char layer.
在过去几十年里,含磷阻燃剂在改善环氧树脂(EP)的阻燃性能方面受到了极大关注。然而,要获得令人满意的阻燃效果,大多数含磷阻燃剂需要高负载量,这会导致阻燃环氧材料的热机械性能变差。为了制备具有优异综合性能的阻燃环氧树脂,以生物质为原料合成了一种糠胺衍生的双二苯基氧化膦衍生物(FA-bis-DOPO)作为阻燃环氧树脂的共固化剂。由于FA-bis-DOPO的刚性及其与环氧基体的反应性,能够提高交联密度,因此它的加入提高了阻燃环氧材料的机械强度、储能模量和玻璃化转变温度。含5.0 wt% FA-bis-DOPO的环氧材料的极限氧指数(LOI)为31.0%,达到UL-94 V-0级,而原始环氧树脂的LOI为23.5%,在UL-94测试中不合格,这表明FA-bis-DOPO具有很高的阻燃效率。此外,锥形量热仪测试结果表明,EP/FA-bis-DOPO-5.0的热释放速率峰值(PHRR)、总热释放量(THR)和总烟释放量(TSP)分别比原始环氧树脂低28.0%、27.3%和9.9%。FA-bis-DOPO的阻燃机理可归因于气相和凝聚相的联合作用机制,即通过淬灭自由基中断燃烧链反应,并通过催化形成完整致密的炭层抑制热解挥发性产物的转移。