端酸酐基支化氟酰亚胺齐聚物流动改性GF/PA66复合材料

Flow modification of GF/PA66 composites induced by anhydride-terminated branched fluorinated polyimide oligomer

  • 摘要: 以4,4′-(六氟异丙烯)二酞酸酐(6FDA)、1,3-双(4′-氨基苯氧基)苯(TPER)和1,3,5-三(4-氨基苯氧基)苯(TAPOB)为单体,冰乙酸和苯甲酸分别作为溶剂和催化剂,采用一步法合成了数均分子量为3.2×103 g/mol、黏流温度为260℃的端酸酐基支化氟酰亚胺齐聚物(BFPI)。由于BFPI分子结构上存在-CF3,表面能较低,倾向于分布在两相界面处。同时BFPI末端酸酐可以与玻璃纤维(GF)表面羟基和尼龙66(PA66)末端氨基反应,增加GF和PA66的界面相互作用,可以显著地促进GF在PA66基体中的分散。以BFPI改性40.0wt% GF增强PA66(GF/PA66)共混体系,与未改性体系相比,添加2.0wt% BFPI可使共混体系平衡扭矩下降63.3%,所制备复合材料拉伸强度和断裂能分别提高20.5%和31.5%,热变形温度提高41.3℃,吸水率下降12.0%,结晶度仅下降1.2%。扫描电镜和光学显微镜对复合材料微观形貌分析表明BFPI使GF更均匀地分散在PA66基体中,GF保留长度从139 μm提升至235 μm,且沿熔体流动方向的取向角从48.45°降低至42.20°。对GF/PA66复合材料进行红外定量和氨基含量分析,一定程度地证明了BFPI的增容作用。对比端酸酐基线性氟酰亚胺齐聚物(FPI),具有支化结构的BFPI对共混体系有更好的流动改性效果,且对复合材料的力学、热和疏水性能改善效果更显著。

     

    Abstract: An anhydride-terminated branched fluorinated polyimide oligomer (BFPI) was synthesized via a one-pot route from 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 1,3-bis(4-aminophenoxy)benzene (TPER) and 1,3,5-tris(4-aminophenoxy)benzene (TAPOB), using glacial acetic acid as the solvent and benzoic acid as the catalyst. The resulting BFPI exhibited a number-average molecular weight of 3.2×103 g/mol and a viscous-flow temperature of 260℃. Owing to the presence of -CF3 groups, BFPI possessed low surface energy and was thus prone to enrich at the glass fiber (GF)/ nylon 66 (PA66) interface. Meanwhile, its terminal anhydride groups could react with the hydroxyl groups on the GF surface and the terminal amino groups of PA66, thereby strengthening interfacial adhesion and promoting GF dispersion in the PA66 matrix. In the modification of a 40.0wt% GF-reinforced PA66 (GF/PA66) blend system with BFPI, compared to the unmodified system, the addition of 2.0wt% BFPI reduced the equilibrium torque of the blend by 63.3%. The resulting composite exhibited a 20.5% increase in tensile strength, a 31.5% increase in fracture energy, a 41.3℃ improvement in heat distortion temperature, a 12.0% reduction in water absorption, and only a 1.2% decrease in crystallinity. Morphological analysis of the composites using scanning electron microscopy and optical microscopy revealed that BFPI enabled a more homogeneous distribution of GF in the PA66 matrix, increased the retained fiber length from 139 μm to 235 μm, and reduced the fiber orientation angle along the melt-flow direction from 48.45° to 42.20°. Quantitative FT-IR analysis and amino end-group measurements further confirmed the compatibilization effect of BFPI. In comparison with the anhydride-terminated linear fluorinated polyimide oligomer (FPI), BFPI with a branched architecture delivered superior flow modification and more pronounced enhancements in the mechanical, thermal, and hydrophobic properties of GF/PA66 composites.

     

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