Synthesis of amidoxime-modifide polyacrylonitrile-β- cyclodextrin nanofiber membranes and its adsorption properties
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摘要: 利用聚丙烯腈(PAN)和β-环糊精(β-CD)原料,采用盐酸羟胺原位偕胺肟改性和静电纺丝技术,一步合成制备出偕胺肟聚丙烯腈(AOPAN)-β-CD纳米纤维膜。以纤维膜的形貌和对铀的吸附量为评价指标,优化了改性制备工艺条件。通过SEM、FTIR、表面张力仪等对纤维的形貌、组成和性能进行表征。结果表明,当氰基与羟胺摩尔比为1∶1、改性时间为2 h时,AOPAN-β-CD纳米纤维膜的形态及纤维直径分布更均匀,纤维直径约为230 nm,纤维膜的吸附容量最大,达到78.62 mg/g。Abstract: Amidoxime polyacrylonitrile (AOPAN)-β-cyclodextrin (β-CD) nanofiber membranes were synthesized in one step using polyacrylonitrile (PAN) and β-CD as raw materials by in-situ amidoxime modification with hydroxylamine hydrochloride and then electrospinning technology. Evaluating by morphology and adsorption capacity, the preparation condition of modification was optimized. The morphology, composition and properties of the membranes were characterized by SEM, FTIR and surface tension meter. The results show that under the optimized modification process conditions, which the molar ratio of cyanogroup to hydroxylamine is 1∶1 and the modification time is 2 h, the morphology distribution of AOPAN-β-CD nanofiber membrane is more uniform and the fiber diameter is about 230 nm, and the adsorption capacity of the fiber membrane reaches 78.62 mg/g.
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Key words:
- amidoximation /
- membranes /
- adsorption characteristic /
- uranium /
- PAN /
- β-CD
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表 1 改性条件对AOPAN-β-CD溶液的可纺性影响
Table 1. Effect of modified condition on the spinnability of AOPAN-β-CD solution
Spinnability Modification time/h 2 4 6 8 10 + + + + + nhydroxylamine∶nKOH 1∶0.15 1∶0.25 1∶0.35 1∶0.45 + + × × ncyano∶nhydroxylamine 3∶1 2∶1 1∶1 1∶2 1∶3 + + + + - Notes:“+”—Easy to electrospinning; “-”—Electrospinning is difficult; “×”—Electrospinning is not possible; ni∶nj—Molar ratio. 表 2 氰基/羟胺摩尔比对AOPAN-β-CD溶液性质及纤维直径的影响
Table 2. Effect of molar ratios of cyanogroup to hydroxylamine on properties of AOPAN-β-CD solution and fiber diameter (Mole ratio of nhydroxylamine∶ nKOH is 1∶0.25 and modification time is 6 h)
ncyano∶nhydroxylamine Viscosity/(mPa·s) Conductivity/(mS·cm−1) Surface Tension/(mN·m−1) Average diameter/nm 3∶1 446.68 719 35.74 400 2∶1 395.57 858 35.91 467 1∶1 426.98 897 30.52 598 1∶2 433.45 1143 36.50 222 表 3 改性时间对AOPAN-β-CD溶液性质及纤维直径的影响
Table 3. Effect of modification time on properties of AOPAN-β-CD solution and fiber diameter (Mole ration of nhydroxylamine∶nKOH is 1∶0.25 and ncyano∶ nhydroxylamine is 1∶1)
Time/h Viscosity/(mPa·s) Conductivity/(mS·cm−1) Surface tension/(mN·m−1) Average diameter/nm 2 512.64 900 34.90 238 4 339.57 1090 30.18 239 8 381.60 964 36.65 494 10 485.61 913 36.41 433 表 4 PAN, AOPAN和AOPAN-β-CD纤维膜的力学性能
Table 4. Mechanical properities of PAN, AOPAN and AOPAN-β-CD
Name Width of membrane/mm Average thickness/mm Tensile strength/MPa PAN 20 0.102 8.673 AOPAN 19 0.065 3.222 AOPAN-β-CD 20 0.125 3.006 -
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