氨基官能化聚乳酸电纺纤维的制备、 表征和应用

doi:10.7503/cjcu20140219

摘要/Abstract

摘要：

通过聚乳酸(PLA)和氨基丙基三乙氧基硅烷(KH550)混合进行静电纺丝制备氨基官能化聚乳酸纳米纤维. 采用滴定法测定了纤维表面氨基含量, 证明当KH550的添加量为3%~13%(质量分数)时, 有19%~26%的氨基出现在纤维的表面. 利用场发射扫描电子显微镜、差示扫描量热(DSC)仪、接触角测试仪和电子拉伸机对纤维形貌、 PLA的玻璃化转变温度和熔点以及纤维膜的亲水性和力学性能进行了表征. 结果表明, KH550的加入可以在电纺纤维表面引入氨基, 同时使纤维直径变细, 使PLA的玻璃化转变温度上升, 熔点下降, 电纺纤维膜的亲水性略有增加, 力学性能有所下降. 通过吸附将金纳米粒子负载到氨基官能化聚乳酸电纺纤维膜上, 得到负载型催化剂, 对硼氢化钠还原对硝基苯酚的反应具有良好的催化活性和重复使用性.

关键词: 聚乳酸, 静电纺丝, 氨基丙基三乙氧基硅烷, 氨基官能化, 催化活性, 纳米纤维

Abstract:

Amine-functionalized poly(lactic acid)(PLA) nanofibers were prepared by co-electrospinning of PLA and aminopropyltriethoxysilane(KH550) in 1,1,1,3,3,3-hexafluoroisopropanol. The contents of amine groups on the surfaces of the fibers were measured by chemical titration. The results show 19%—26% of total amine groups appeared on the fiber surfaces when 3%—13% of KH550 to PLA is added. The amine-functionalized PLA nanofibers were also characterized by field emission scanning electron microscopy, differential scanning calorimetry(DSC), contact angle measurements and uniaxial tensile tests. It has been shown that the addition of KH550 can introduce amine groups on PLA fiber surfaces, meantime the fiber diameter decreases, T_g of PLA increases, T_m of PLA decreases, the hydrophilicity of the fiber mat slightly increases and its mechanical properties decreases. Au nanoparticles were adsorbed on the surface of amine-functionalized PLA nanofibers, which showed good catalytic activity and reusability for the reduction of 4-nitrophenol.

Key words: Poly(lactic acid), Electrospinning, Aminopropyltriethoxysilane(KH550), Amine-functionalization, Catalytic activity, Nanofiber

中图分类号:

O631

TrendMD:

熊曦, 李强, 张绪成, 于建, 郭朝霞. 氨基官能化聚乳酸电纺纤维的制备、表征和应用. 高等学校化学学报, 2014, 35(6): 1323.

XIONG Xi, LI Qiang, ZHANG Xucheng, YU Jian, GUO Zhaoxia. Preparation, Characterization and Application of Amine-functionalized Poly(lactic acid) Electrospun Fibers^†. Chem. J. Chinese Universities, 2014, 35(6): 1323.

图/表 10

Fig.1 FE-SEM images of electrospun PLA/KH550 fibersMass fraction of KH550(%): (A) 0; (B) 3; (C) 8; (D) 13.

Table 1 Diameters, surface NH2 contents and contact angles of electrospun PLA/KH550 mats

Sample	Fiber diameter/μm	Surface NH₂ content/(mmol·g^-1)	Ratio of NH₂ on surface(%)	Contact angle/(°)
Pure PLA	0.90±0.14	0	0	129.4±1.8
PLA/3%KH550	0.40±0.14	0.025	19.1	115.2±1.6
PLA/8%KH550	0.39±0.07	0.074	22.2	107.3±1.8
PLA/13%KH550	0.28±0.08	0.141	26.1	102.2±0.9

Table 2 Thermal properties and crystallinity of PLA/KH550 electrospun mats

Sample	T_g/℃	T_m/℃	Δ $H m a$ /(J·g^-1)	$X c b$ (%)
Pure PLA	43.26	152.65	11.5	12.4
PLA/3%KH550	50.95	146.62	27.1	29.2
PLA/8%KH550	52.19	143.90	25.1	27.0
PLA/13%KH550	52.83	142.36	23.6	25.4

Table 2 Thermal properties and crystallinity of PLA/KH550 electrospun mats

Sample	T_g/℃	T_m/℃	Δ $H m a$ /(J·g^-1)	$X c b$ (%)
Pure PLA	43.26	152.65	11.5	12.4
PLA/3%KH550	50.95	146.62	27.1	29.2
PLA/8%KH550	52.19	143.90	25.1	27.0
PLA/13%KH550	52.83	142.36	23.6	25.4

Fig.2 DSC curves of PLA/KH550 electrospun matsa. PLA; b. PLA/3%KH550; c. PLA/8%KH550; d. PLA/13%KH550.

Fig.3 Stress-strain curves of PLA/KH550 electrospun matsa. PLA; b. PLA/3%KH550; c. PLA/8%KH550; d. PLA/13%KH550.

Table 3 Mechanical properties of PLA/KH550 electrospun mats

Sample	Thickness/mm	Modulus/MPa	Tensile strength/MPa	Elongation at break(%)
Pure PLA	0.144±0.001	63.6±10.2	3.9±0.1	122.8±6.9
PLA/3%KH550	0.099±0.014	29.4±5.5	2.7±0.1	34.2±0.3
PLA/8%KH550	0.075±0.005	27.6±6.1	1.5±0.1	14.4±0.9
PLA/13%KH550	0.105±0.004	46.6±8.4	2.0±0.1	6.9±1.1

Fig.4 FE-SEM images of Au nanoparticles adsorbed on PLA/KH550 fibersMass fraction of KH550(%): (A) 3; (B) 8; (C) 13.

Fig.5 TGA curves of Au-containing PLA/KH550 fibers

Fig.6 UV-Vis spectra of 4-nitrophenol solution with Au nanoparticles-adsorbed on electrospun PLA/KH550 fibers containing different amounts of KH550 as catalystMass fraction of KH550(%): (A) 3; (B) 8; (C) 13; (D) without catalyst.

Fig.7 Absorbance vs. reaction time curves(A) and catalytic activity of PLA/13%KH550 sample in 3 times(B)

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