交联稳定化对聚酰亚胺基石墨纤维结构和性能的影响

Effect of crosslinking method on the microstructures and properties of polyimide-based graphite fibers

  • 摘要: 有机纤维中分子链之间的交联稳定化是炭纤维制备过程中的重要工艺。本文首先制备了一种带羧基侧链的聚酰亚胺(PI)纤维,然后经羧基间氢键的物理交联及与1,4-丁二醇发生化学交联制备了两种不同交联方式的共聚PI纤维,最后经炭化、石墨化制备了PI基石墨纤维。借助于TG-DSC,XRD等测试方法对两种交联方式处理的共聚PI纤维进行表征,发现物理交联能显著提高共聚PI纤维的炭化收率,石墨化收率及热稳定性,并且物理交联PI基石墨纤维石墨化程度和热导率优于化学交联。随着3,5-二氨基苯甲酸(DABA)含量增加,物理交联PI基石墨纤维的石墨化程度和热导率逐渐增加,DABA含量为5%的纤维石墨化程度最优,含量10%的热导率最高为245.6 W·m-1·K-1

     

    Abstract: Different polyimide (PI) fibers with and without carboxyl groups on the polymer chain were prepared by dry-jet wet spinning using 1,2,4,5-benzene tetracarboxylic dianhydride (PMDA), p-phenylenediamine (p-PDA) and 3,5-diaminobenzoic acid (DABA) as the PI monomers with a PMDA/(DABA+ p-PDA) mass ratio of 1.02:1 and different DABA/p-PDA mass ratios. The PI fibers were chemically crosslinked with 1,4-butanediol to improve their thermal stability. The PI fibers before and after chemical crosslinking were carbonized at 1400℃ for 1 h and graphitized at 2800℃ for 1 h to prepare graphite fibers. Results indicate that the crosslinking by hydrogen bonding between carboxyl groups significantly increased the thermal stability and increased the carbonization and graphitization yields of the PI fibers. The graphitization degree and thermal conductivity of the graphite fibers from the PI with carboxyl groups are higher than those from the corresponding chemically crosslinked ones. The graphitization degree and thermal conductivity increase with the DABA/p-PDA ratio. The highest degree of graphitization (97.9%) was obtained at a DABA/p-PDA ratio of 5:95 while the highest thermal conductivity (245.6 W/(m·K)) was obtained at a DABA/p-PDA ratio of 10:90.

     

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