静电纺丝纤维对煤基气体污染物脱除研究进展

煤在气化和燃烧过程中产生的气体污染物和颗粒物会转移到合成气和空气中,从而产生设备腐蚀和环境污染等问题。静电纺丝纤维具有可调控的、超细的直径,多孔的结构,超高的比表面积,可设计的形貌以及易于表面修饰等优点,在气体污染物脱除领域有着巨大的应用价值。介绍了静电纺丝的基本原理和发展现状,综述且简要分析了静电纺丝纳米纤维材料在PMs、CO₂、NO_x、H₂S、SO₂和VOCs等气体污染物脱除方面的应用及研究现状。最后,对电纺纤维在气体污染物脱除领域中更广泛、更深入的应用前景进行了展望。     

The mechanism of the controlled deposition of electrospun fibers

The controlled deposition of electrospun fibers means that the electrospun fibers can be collected in a limited and specified area and can present better applications in the fields of medical treatment, garment making, and 3D printing. In order to study the mechanism of the controlled deposition of electrospun fibers, simulation and experimental methods were used. Specifically, in the electrospinning experiment, circular copper sheets of different diameters were used as collectors. The effect of different collector areas on the morphology of fiber deposition was discussed. The electric field distribution of electrospinning with different specifications of collectors was simulated correspondingly. The experimental results show that, as compared to the traditional large flat collector, the area where the electrospun fibers are deposited is significantly reduced when a smaller circular copper plate was used as a collector. The smaller the area of the collector, the more the fibers tend to deposit at the center area of the collector, and the more likely the morphology of the product formed by the fiber deposition to exhibit a center protrusion shape. The controlled deposition of the electrospun fiber technology can provide more opportunities for the application of the electrospinning technology.     

端胺基聚丁二烯的合成与表征

采用阴离子聚合法合成了端羟基聚丁二烯,通过端基转化法将羟基转化成胺基,从而合成了端胺基聚丁二烯,通过红外光谱（IR）、核磁共振（1H-NMR）、凝胶渗透色谱（GPC）等对其进行了表征。结果表明,所合成的端胺基聚丁二烯相对分子质量分布较窄（≤1.10）,平均官能度接近2,且微观结构可调;通过羟基值与胺基值的测定表明,端基转化率大于98%。     

紫外光辐照交联EVA的制备及表征

采用紫外辐照技术制备了交联乙烯-L酸乙烯酯共聚物(XLEVA)。研究了实验温度、实验气氛、试样厚度及辐照时间等条件以及光引发剂、光交联剂的种类和浓度等因素对凝胶含量的影响。结果表明,辐照时间为2 min,温度为100℃时,交联效果较好,在此条件下,辐照氛围及试样厚度对交联反应影响不明显。二苯甲酮的引发效果优于安息香二甲醚,三羟甲基丙烷三丙烯酸酯的助交联效果最佳,两者的最佳含量均为1%,此时XLEVA的凝胶含量可达到86.48%。     

Changes in orientation caused by UV irradiation of nylon 6 fibers

The effect of UV radiation on the structural parameters that relate to the optical properties of nylon 6 fibers are investigated using interferometry. When the optical parameters are known, we can use them to calculate various orientation functions given by Hermans and de Vries. The properties of concern are the surface reflectivity, transparency, stress optical coefficient, stress due to UV irradiation, optical configuration parameter, segment anisotropy, dielectric constant, and susceptibility. The number of molecules per unit volume, isotropic refractive index, polarizability of a monomer unit, specific refractivity of the dielectric (along and across the fiber axis) and the form birefringence were obtained. The results are established by relationships designed to relate the calculated structural parameters to the time of exposure. The study demonstrates how the structural parameters change during exposure to UV radiation. Illustrations are given using graphs and microinterferograms. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3202–3211, 2003     

Effect of lewis acids on cure kinetics and mechanical properties of hydroxyterminated polybutadiene polymers

The effect of two Lewis acids, viz. BF₃ and AlCl₃ on the cure reaction of hydroxy-terminated polybutadiene: toluene diisocyanate systems has been studied in order to evaluate them as possible pot-life extenders in solid propellant formulations. The enthalpy of the cure exotherm, evaluated from DSC curves, did not show any dependence on the concentration of the two acids. The kinetic parameters for the cure reaction showed an increase in both cases indicating the effectiveness of the acids as reaction retardants. However, BF₃ is not a suitable candidate for pot-life extension, because of its adverse effect on the elongation at break of the cured HTPB samples. The coefficient of thermal expansion is unaffected by the two additives, probably because of their negligible influence on the cross-link density of the cured network.     

Alignment of electrospun polystyrene with an electric field

Polystyrene (PS) with a concentration of 20% by weight in THF/DMF was electrospun on a flat sheet collector. At a concentration of THF above 75%, blocking at the needle tip caused bead formation. However, a nice fiber mat was obtained with the 75/25 THF/DMF. Moreover, at a traveling distance of 10 and 15 cm and voltages from 10 to 16 kV, the PS fibers exhibited alignment. This alignment was reproducible when voltage stabilizer was connected to the voltage supply. This suggested that the uniformly positive charges arising from external voltage interacted with the aromatic rings on the PS chain, yielding a uniform dipole moment. As a result, during jet traveling, the solvent evaporated and the molecules were oriented and frozen at the ground collector. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Functionality distribution and crosslink density of hydroxyl-terminated polybutadiene

A novel approach is proposed for estimating the average molecular weight between crosslinks (M?_c) from the functionality distribution of hydroxyl-terminated polybutadiene ( HTPB ). The functionality distribution of four free-radically polymerised HTPB prepolymers of varying hydroxyl content and molecular weight was determined by a combination of preparative and analytical gel permeation chromatography. The gumstock properties of the samples cured with stoichiometric amounts of toluene diisocyanate were not correlatable with the relative amounts of difunctional chain extender and multifunctional crosslinker present, unlike the case of HTPB with similar hydroxyl content and molecular weight. However, the mechanical properties and sol content could be correlated with the average molecular weight between crosslink sites, M?_c, of the cured polymer. The M?_c values derived by our method compare well with those of classical methods, and the observed differences are attributed to segmental entanglement. These M?_c values give consistently good correlation with all the gumstock properties, confirming the validity of our approach and the soundness of the techniques developed for the determination of the functionality distribution of HTPB .     

三臂星形端羟基聚丁二烯的阴离子合成及其表征

以叔丁基二甲基硅氧基丙基锂为引发剂,环己烷为溶剂进行阴离子聚合合成三臂星形端羟基聚丁二烯。采用凝胶渗透色谱(GPC)和1H-NMR方法表征了聚合物相对分子质量及其分布、支化度、平均官能度和主链微观结构。研究结果表明,三臂星形端羟基聚丁二烯的相对分子质量分布指数≤1.1,平均官能度和支化度均接近3。     

Studies on the electrospun submicron fibers of SIS and its mechanical properties

The submicron fibers were prepared via electrospinning the styrene–isoprene–styrene (SIS) triblock copolymer from a pure solvent of tetrahydrofuran (THF) and a mixed solvent of THF and N, N‐dimethylformamide (DMF). The addition of DMF to THF resulted in a beneficial effect on the fiber formation and the electrospinnability. The obtained results revealed that the fibers were only formed in a narrow solution concentration range of 8–15 wt %; the morphology, diameter, structure, and mechanical performance of as‐spun fibers from PS and SIS solutions were affected by the composition weight ratio and the solution properties; and those from the solution at the intermediate concentration of 10 wt % exhibited a maximum tensile strength and strain at break. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The effect of UV irradiation on the electrospun PCL/TiO2 composites fibers

The effect of UV irradiation and micro‐ and nano‐TiO₂ as well as titanate nanotubes (TiNT) on the phase morphology and thermal properties of the electrospun PCL composite fibers was investigated. Polycaprolactone (PCL)/TiO₂ (micro‐ and nano‐TiO₂ as well as titanate nanotubes) composite fibers were prepared by electrospinning a polymer solution. The PCL and PCL/TiO₂ composite fibers were exposed to UV light at irradiation times of 5 and 10 days. After UV irradiation the crystallinity of the electrospun PCL/TiNTcomposite fibers increased because of the large specific surface area of TiNT. The thermal stability of the PCL/TiNT electrospun composite fibers increased due to the formation of crosslinking structure after UV irradiation. The SEM analysis suggests that after UV radiation the fibers showed high degree of degradation due to the high number of fibers breakages and fibers surface voids. The results of FTIR spectroscopy confirmed that the TiO₂ particles enhance the degradation process because of their photocatalytic activity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43539.     

Modification of aqueous polyurethane dispersions by polybutadiene

Aqueous polyurethane (PU) adhesives are nontoxic and nonflammable and do not pollute the air. However, they have low adhesive strengths compared to solvent‐based PU adhesives because of a low affinity with rubber substrates. In this study, PU adhesives were synthesized from isophorone diisocyanate with dimethylol propionic acid as the ionic center in the main chain, triethylamine as the neutralization agent, and hydrazine as the chain extender. The polyol was modified with hydroxyl‐terminated polybutadiene (HTPB) and hydroxyl‐terminated acrylonitrile–butadiene copolymer (HTBN). The effect of the HTPB and HTBN content on the adhesive strength was investigated. The effect of the prepolymer molecular weight was also investigated. Increases in the HTPB and HTBN contents led to an increase in the adhesive strength because of the increase of chemical affinity between the adhesive and the substrate. The adhesive strength increased as the prepolymer molecular weight increased. This was due to an increase in the tensile strength and modulus. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1062–1068, 2005     

Fabrication and characterization of zein/viscose textibe fibers

Azlons are increasingly concerned for their excellent performance properties and biodegradation. A kind of novel azlon, zein/viscose textibe fibers, were fabricated by wet‐spinning of zein and cellulose sulfonate blended solution. Some parameters that determine the fabrication process were optimized. The structure and properties of zein/viscose fibers were characterized, and compared with those of common viscose fibers. Dry breaking tenacity of zein/viscose fibers was 2.02 CN/dtex, whereas dry breaking elongation was 16.6%. Mechanical properties of zein/viscose fibers were a little better than common viscose fibers. The moisture regain rate of zein/viscose fibers was 14.1%, similar to that of viscose fibers. From the microstructure of zein/viscose fiber, viscose acted as framework and zein was accreted to viscose. The content of protein was 14.48% in zein/viscose fibers. The basic chains of zein and viscose were not changed by blended spinning, so the fibers had advantages of both zein and viscose. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of biodegradable hydroxyethylcellulose cryogels by UV irradiation

Biodegradable macroporous hydroxyethylcellulose (HEC) cryogels of good quality and high gel fraction yield (95%) were synthesized via a facile method. The latter involved a relatively fast preparation of homogeneous semidilute solution of polymer and photoinitiator, (4-benzoylbenzyl)trimethylammonium chloride, followed by freezing at a defined negative temperature, an extremely short UV irradiation and subsequent thawing. HEC cryogels were successfully prepared also by using H₂O₂ as a photoinitiator. The effects of the temperature of freezing, the HEC molecular weight and the concentration of HEC solution on the cross-linking efficiency, the swelling ratio and the enzymatic degradation of HEC cryogels were investigated. Due to the cryoconcentration phenomenon, cryogels are formed at substantially low initial concentrations of the studied polymers. The highest values of gel fraction yield are achieved in the 1-2 wt.% concentration range at −20 °C. As a rule, the higher the molecular weight, the greater the gel fraction yield of the resulting cryogels. Scanning electron microscopy (SEM) analysis reveals that the interior structure of HEC cryogels is completely different from the conventional HEC hydrogels. HEC cryogels undergo decomposition by the action of cellulase enzyme, however, due to their specific morphology, the rate of degradation is slower compared to the conventional HEC hydrogel of similar gel fraction yield.     

Fabrication and characterization of electrospun fibrous nanocomposite scaffolds based on poly(lactide‐co‐glycolide)/poly(vinyl alcohol) blends

Tissue engineering involves the fabrication of three‐dimensional scaffolds to support cellular in‐growth and proliferation. Ideally, the scaffolds should be similar to the native extracellular matrix (ECM). Electrospun polymer nanofibrous scaffolds are appropriate candidates for ECM mimetic materials since they mimic the nanoscale properties of ECM. Electrospun polymer nanocomposites based on poly(lactide‐co‐glycolide) (PLGA)/poly(vinyl alcohol) (PVA) and organically modified montmorillonite (OMMT) were prepared by a solution intercalation technique followed by electrospinning. The morphology of fibrous scaffolds based on these nanocomposites was investigated using scanning electron microscopy. The scaffolds showed highly porous structure within the nanofibres of diameters ranging from 400 to 700 nm. X‐ray diffractometry gave evidence of good dispersion of the OMMT in the blends with exfoliated morphology. Measurements of the water uptake and water contact angle of the fibrous scaffolds indicated significant improvement in the hydrophilicity of the scaffolds. Evaluations of the mechanical properties and unrestricted somatic stem cell culture of the electrospun fibrous nanocomposite scaffolds revealed that the PLGA90/PVA10/1.5% OMMT and PLGA90/PVA10/3% OMMT samples are the most useful from the tissue engineering application viewpoint. Copyright © 2010 Society of Chemical Industry     

静电纺丝抗菌聚氨酯纳米纤维的结构与性能

在聚氨酯/四氢呋喃-N,-二甲基甲酰胺(PU/THF-DMF)溶液中分别添加质量分数为5%的TiO_2-Ag,HM-98,三氯均二苯胺(TCC),4-氯-3,5-二甲基苯酚(PCMX),2,4,4'-三氯-2'-羟基二苯酚(DP 300),ε-聚赖氨酸(ε-PLYS)抗菌剂通过静电纺丝技术制备了PU抗菌纳米纤维,并对其性能和结构进行了研究。结果表明:含ε-PLYS,HM-98,TiO_2-Ag,DP300抗菌剂的抗菌PU纳米纤维对金黄色葡萄球菌和大肠杆菌的抗菌效果较为优良,抗菌率均达到了99.9%以上,TCC、PCMX抗菌剂的抗菌效果较差;添加HM-98抗菌剂降低了纺丝溶液的可纺性,但纤维直径有所下降;抗菌剂在PU中的分散性好。     

Crosslinking of isocyanate functional acrylic latex with telechelic polybutadiene. I. Synthesis and characterization

An ambient curable isocyanate functional acrylic latex was synthesized by incorporating dimethyl meta-isopropenyl benzyl isocyanate (TMI®), an isocyanate monomer, into styrene/n-butyl acrylate copolymer. An artificial latex of amino-terminated telechelic polybutadiene was prepared and blended with the acrylic latex as a curing agent. The isocyanate content in the blended latex was determined by titration and FTIR measurements. The latex blend properties, in terms of particle size and latex viscosity, and the latex film properties, in terms of stress–strain behavior and solvent swelling behavior, showed no significant change after 30 days' storage of the latex blend at 50°C. The good storage stability was attributed to the stable nature of the latex blend in which there was little chance for the isocyanate-containing particles to come into contact with the curing agent particles, thus preventing premature contact of the acrylic chains with the telechelic chains. The reactivity of different functional groups in the telechelic polymer was studied; the amino group was found to be the most reactive toward the TMI. In addition, a shorter chain telechelic crosslinker was found to result in a higher degree of crosslinking, but this was more intraparticle than interparticle in nature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 965–975, 1998     

立构三嵌段聚丁二烯的合成及其加氢产物的性能

用α -甲基萘锂作为双官能团引发剂 ,通过丁二烯在环己烷中进行负离子聚合 ,达到一定转化率后 ,加入极性改性剂 ,继续聚合至结束 ,合成了不同嵌段比的 1,2 - 1,4 - 1,2立构三嵌段聚丁二烯 ,并用三异丁基铝及 2 -乙基己酸钴作为加氢催化剂 ,制备了氢化立构嵌段聚丁二烯。考察了不同极性改性剂及其用量和聚合温度对聚丁二烯微结构的影响 ,分析表征了立构嵌段聚丁二烯及氢化物。结果表明 ,当引发剂用量一定时 ,极性改性剂 /引发剂的摩尔比越大 ,1,2 -链节摩尔分数越高 ;当加入极性改性剂时 ,1,2 -链节摩尔分数随聚合温度的降低而增加 ,1,2 -嵌段的生成宜控制在 0℃ ;立构三嵌段聚丁二烯的相对分子质量分布很窄 ,且存在 2个玻璃化转变温度。氢化物的结晶度为 30 % ,为 (1-丁烯 -乙烯 - 1-丁烯 )三嵌段共聚物 ,呈现热塑性弹性体的行为 ;当其特性黏数大于 2 0dL·g-1,且聚1-丁烯的质量分数为 2 0 %～ 6 0 %时 ,其力学性能较好。     

Poly(ethylene oxide)/polybutadiene based IPNs synthesis and characterization

Interpenetrating polymer networks (IPNs) were prepared from hydroxytelechelic polybutadiene (HTPB) and poly(ethylene oxide) (PEO) via an in situ process. The PEO network was obtained by free radical copolymerization of poly(ethylene glycol) methacrylate and dimethacrylate. Addition reactions between HTPB and a pluri-isocyanate cross-linker (Desmodur^® N3300) led to the HTPB network. Polymerization kinetics were followed by Fourier transform spectroscopy in the near and middle infrared. Mechanical properties and the IPN morphology were investigated by dynamic mechanical analysis and transmission electron microscopy. The relation between the formation rates of the two networks and the IPN final morphology is discussed.     

Mechanical,thermal, and dielectric properties of SiCf/SiC composites reinforced with electrospun SiC fibers by PIP

Electrospun unidirectional SiC fibers reinforced SiC_f/SiC composites (e-SiC_f/SiC) were prepared with ∼10% volume fraction by polymer infiltration and pyrolysis (PIP) process. Pyrolysis temperature was varied to investigate the changes in microstructures, mechanical, thermal, and dielectric properties of e-SiC_f/SiC composites. The composites prepared at 1100 °C exhibit the highest flexural strength of 286.0 ± 33.9 MPa, then reduced at 1300 °C, mainly due to the degradation of electrospun SiC fibers, increased porosity, and reaction-controlled interfacial bonding. The thermal conductivity of e-SiC_f/SiC prepared at 1300 °C reached 2.663 W/(m∙K). The dielectric properties of e-SiC_f/SiC composites were also investigated and the complex permittivities increase with raising pyrolysis temperature. The e-SiC_f/SiC composites prepared at 1300 °C exhibited EMI shielding effectiveness exceeding 24 dB over the whole X band. The electrospun SiC fibers reinforced SiC_f/SiC composites can serve as a potential material for structural components and EMI shielding applications in the future.