基于电纺丝与ATRP聚合技术构建多功能性薄膜
摘要
电纺丝技术高效方便地制备出具有多孔结构的纳米纤维薄膜材料,对纳米纤维表面进行化学修饰,可进一步扩大所制备薄膜材料在传感、催化、分离等领域的应用。近年来,电纺丝的表面修饰受到研究者的广泛关注,文献已经报道的修饰方法包括“click”反应、电化学沉积和等离子体处理等。在本文中,我们成功的制备出纤维表面含有聚合引发位点的二氧化硅纳米纤维薄膜材料,纳米纤维表面含有的引发位点的密度与文献中通过溶液沉积法得到的基体表面的引发位点密度近似,而且由纳米纤维构成的薄膜有一定的机械强度和化学稳定性,通过原子转移自由基活性聚合(ATRP),可以根据自己的需要将不同性质的聚合物刷子接枝在电纺丝表面,刷子是调控表面性质一种常用的方法。本文中,我们将三种不同性能聚合刷子接枝于纤维表面。获得了具有特异功能的薄膜材料。
首先,我们成功在电纺丝表面合成离子液体的刷子,将离子液体的特性和电纺丝特性有机的结合在一起,获得了一种具有可调节性的功能薄膜体系。通过调节对抗离子,膜的表面结构很容易被调控。这种薄膜可以用作电化学的开关,改变对抗离子,膜孔洞的亲疏水性发生变化,由亲水逐渐变为疏水,薄膜的孔洞逐渐排斥水分子,电化学信号随之改变,当对抗离子为疏水性最强的三氟甲磺酸根离子时,孔洞关闭,而且此过程是可逆的,关闭的孔洞可以重新打开。我们又将具有电活性的对抗离子磷钨酸根通过离子交换方法固定在膜表面,使膜具有电活性。其次,我们又分别在电纺丝表面合成除了聚(乙烯基吡啶)和聚(甲基丙烯酸)刷子,这类刷子修饰的电纺丝膜可以用作制备金属有机复合材料的支架,这种薄膜材料在气体分离方面有广泛的应用。
在本文中,我们运用了各种表征手段,如核磁共振,透射红外,反射红外,扫描电子显微镜,透射电子显微镜和X射线光电子能谱等。
Electrospinning is novel and efficient fabrication method that can produce fibrous membranes with fiber diameters ranging from several micrometers down to tens of nanometers. Surface functionalization of electrospun fibers is a versatile method to extend its application in sensors, filtration, catalysis and so on. In this work, we electrospun SiO2 nanofibers containing certain similar density of initiator site on surface, comparable to that prepared by using post-derivated solution deposition approach. All kinds of brushes possibly grafted from the surface of nanofibers with atom transfer radical polymerization(ATRP). In this work, three different brushes separately synthesized on the surface of nanofibers, at the same time, functionalized membrane were achieved.
Poly (ionic liquid) brushes were successfully grafted from the electrospun SiO2 nanofiber surface. Combining the unique properties of ionic liquid and electrospun nanofibrous mat, this hierarchically structured membrane provides a useful platform for developing functionalized membrane systems. With counteranion exchange of the attached poly (ionic liquid) brushes, the properties and functionality of the prepared membrane can be easily adjusted. Such membrane was served as anion-directed molecular gating system. With counteranion exchange, the surface properties of the membrane was reversibly altered between hydrophilic to hydrophobic, which make pores withdraw or expel solvent molecules (H2O), thus controlling the transport of probe molecules through membrane. As further example, electroactive polyoxometalate (POM) units were incorporated into membrane through simple conteranion exchange, and functionalized membrane with electroactivity was also achieved. Poly (methacrylic acid) and poly (4-vinyl pyridine) were also separately grafted from electrospun membrane, which provide a platform for developing Metal -Organic Framework (MOF) Membrane. The electrospun membrane coated MOF potentially could be applied in gas sorption.
In this work, various characterization techniques including infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and electrochemical measurement were used to characterize the related membrane systems.
首先,我们成功在电纺丝表面合成离子液体的刷子,将离子液体的特性和电纺丝特性有机的结合在一起,获得了一种具有可调节性的功能薄膜体系。通过调节对抗离子,膜的表面结构很容易被调控。这种薄膜可以用作电化学的开关,改变对抗离子,膜孔洞的亲疏水性发生变化,由亲水逐渐变为疏水,薄膜的孔洞逐渐排斥水分子,电化学信号随之改变,当对抗离子为疏水性最强的三氟甲磺酸根离子时,孔洞关闭,而且此过程是可逆的,关闭的孔洞可以重新打开。我们又将具有电活性的对抗离子磷钨酸根通过离子交换方法固定在膜表面,使膜具有电活性。其次,我们又分别在电纺丝表面合成除了聚(乙烯基吡啶)和聚(甲基丙烯酸)刷子,这类刷子修饰的电纺丝膜可以用作制备金属有机复合材料的支架,这种薄膜材料在气体分离方面有广泛的应用。
在本文中,我们运用了各种表征手段,如核磁共振,透射红外,反射红外,扫描电子显微镜,透射电子显微镜和X射线光电子能谱等。
Electrospinning is novel and efficient fabrication method that can produce fibrous membranes with fiber diameters ranging from several micrometers down to tens of nanometers. Surface functionalization of electrospun fibers is a versatile method to extend its application in sensors, filtration, catalysis and so on. In this work, we electrospun SiO2 nanofibers containing certain similar density of initiator site on surface, comparable to that prepared by using post-derivated solution deposition approach. All kinds of brushes possibly grafted from the surface of nanofibers with atom transfer radical polymerization(ATRP). In this work, three different brushes separately synthesized on the surface of nanofibers, at the same time, functionalized membrane were achieved.
Poly (ionic liquid) brushes were successfully grafted from the electrospun SiO2 nanofiber surface. Combining the unique properties of ionic liquid and electrospun nanofibrous mat, this hierarchically structured membrane provides a useful platform for developing functionalized membrane systems. With counteranion exchange of the attached poly (ionic liquid) brushes, the properties and functionality of the prepared membrane can be easily adjusted. Such membrane was served as anion-directed molecular gating system. With counteranion exchange, the surface properties of the membrane was reversibly altered between hydrophilic to hydrophobic, which make pores withdraw or expel solvent molecules (H2O), thus controlling the transport of probe molecules through membrane. As further example, electroactive polyoxometalate (POM) units were incorporated into membrane through simple conteranion exchange, and functionalized membrane with electroactivity was also achieved. Poly (methacrylic acid) and poly (4-vinyl pyridine) were also separately grafted from electrospun membrane, which provide a platform for developing Metal -Organic Framework (MOF) Membrane. The electrospun membrane coated MOF potentially could be applied in gas sorption.
In this work, various characterization techniques including infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and electrochemical measurement were used to characterize the related membrane systems.
引文
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