Preparation and performance of braid‐reinforced poly(vinyl chloride) hollow fiber membranes

A novel braid‐reinforced (BR) poly(vinyl chloride) (PVC) hollow fiber membrane was fabricated via dry‐wet spinning process. The mixtures of PVC polymer solutions were uniformly coated on the tubular braid which contained polyester (PET) and polyacrylonitrile (PAN) fibers. The influences of braid composition on structure and performance of BR PVC hollow fiber membranes were investigated. The results showed that the prepared BR PVC hollow fiber membranes were composed of two layers which contained separation layer and tubular braid supported layer when the PET and PET/PAN hybrid tubular braids were used as the reinforcement. But the sandwich structure appeared when the PAN tubular braid was used as the reinforcement, which revealed outer separation layer, tubular braid supported layer and the inner polymer layer. The BR PVC hollow fiber membranes that prepared by PET/PAN hybrid tubular braid had favorable interfacial bonding state compared with the membrane prepared by pure PET or PAN tubular braid. The pure water flux of the BR PVC hollow fiber membranes that prepared by the PET/PAN hybrid tubular braid were lower than that prepared by pure PET or PAN tubular braid, but the rejection of Bovine serum albumin was opposite. The tensile strength of prepared BR PVC hollow fiber membrane was higher than 50 MPa. Both of the tensile strength and elongation at break decreased with the increase of the PAN filaments in the PET/PAN hybrid tubular braid. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45068.     

Preparation and membrane performance of poly(ethylene-co-vinyl alcohol) hollow fiber membrane via thermally induced phase separation

Poly(ethylene-co-vinyl alcohol) (EVOH) hollow fiber membranes with ultrafiltration performance were prepared from EVOH/glycerol systems via thermally induced phase separation (TIPS). The diluent glycerol was used as bore liquid to make a lumen of the hollow fiber for the purpose of prevention of the diluent evaporation and the larger pores formation at the inner surface of the hollow fiber. The obtained hollow fiber membranes showed asymmetric structures with skin layer near the outer surface, the larger pores just below the skin layer and the smaller pores near the inner surface. The formation of the larger pores near the outer surface was due to the enhanced pore growth by the water penetration. Some primary factors affecting the structure and performance of the membranes such as ethylene content (EC) in EVOH, cooling water bath temperature and take-up speed were studied extensively. The water permeability can be improved by increasing the water bath temperature and the take-up speed and by decreasing the EC. Both the pore size at the outer surface and the connectivity between the pores have to be considered together to understand the experimental result of the water permeability and the solute rejection.     

Preparation of poly(phthalazinone ether sulfone ketone) hollow fiber membrane for gas separation

Poly(phthalazinone ether sulfone ketone) (PPESK) asymmetric hollow fiber membranes for gas separation were prepared by dry/wet phase inversion technique. The effects of various preparation conditions such as solvent, nonsolvent-additives(NSA), PPESK concentration, and air gap on the membrane performance were studied. The heat resistance of the PPESK hollow fiber membrane was also examined. The hollow fiber membrane prepared from solvent with stronger solubility showed low gas permeation and high O₂/N₂ selectivity due to the denser skin layer. Hollow fiber membrane made from PPESK/DMAc/EtOH/THF system had thicker skin layer than that made from PPESK/DMAc/GBL system with the same ratio of near-to-cloud-point of NSA, which resulted in the higher O₂/N₂ selectivity. Along with the increase of NSA content, the gas permeation increased and the O₂/N₂ selectivity decreased. The O₂/N₂ selectivity of hollow fiber membranes made from PPESK/DMAc/GBL and PPESK/DMAc/EtOH/THF systems were 4.9 and 4.8 respectively, when the membrane forming systems contained appropriate content of NSA. The high polymer concentration resulted in low gas permeation and high O₂/N₂ selectivity. When the air gap was excessively long, the membrane performance dropped because of the damage to the dense skin layer. There was no significant drop on the membrane performance when the operation temperature was elevated to 90°C. The average O₂/N₂ selectivity was higher than 3.0 at 70°C during a long period of 55 days' test time. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Poly(D,L‐lactide‐co‐glycolide)/poly(ethylenimine) blend matrix system for pH sensitive drug delivery

Poly(D ,L ‐lactide‐co‐glycolide) (PLGA) and poly(ethylenimine) (PEI) were blended and found to form a homogeneous pH sensitive matrix for drug release. Differential scanning calorimetry (DSC) studies of the PLGA/PEI blends showed a single glass transition temperature at all compositions. Fourier transform infrared spectroscopy (FTIR) demonstrated that the PLGA carbonyl peak at 1760 cm^?1 shifted to 1666 cm^?1 as a result of amide bond formation between the two polymers. This was confirmed by ¹³C nuclear magnetic resonance studies. A PLGA/PEI matrix of 90/10 weight ratio was chosen for evaluation for controlled drug release. Both hydrophobic β‐lapachone and hydrophilic rhodamine B showed pH dependent release profiles with faster release kinetics at lower pH values. The observed pH sensitive drug release was mainly attributed to two factors, pH dependent swelling and protonation of the PEI‐PLGA matrix. These results demonstrate utility of a PLGA/PEI matrix and its potential application in pH responsive drug delivery. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 89–96, 2006     

Assignment of 1H NMR spectrum and investigation of oxidative degradation of poly(ethylenimine) using 1H and 13C 1‐D and 2‐D NMR

The ¹H NMR spectrum of poly(ethylenimine) (PEI) has been assigned using two‐dimensional NMR correlation with the previously established assignment of the ¹³C spectrum. The oxidative thermal and UV degradation of PEI has been studied using mass loss measurements, and NMR and Fourier transform infrared spectroscopy. Analysis of the spectra of the degradation products shows that the degradation process may readily be monitored, particularly by ¹³C NMR. The major products are formamide and other amide groups which may be understood in terms of chain scission and dehydration reactions of hydroperoxides. Copyright © 2006 Society of Chemical Industry     

非溶剂添加剂对聚醚砜酮中空纤维纳滤膜结构和性能的影响

以新型杂萘联苯聚醚砜酮(PPESK)为膜材料,N-甲基-2-吡咯烷酮(NMP)为溶剂,乙二醇甲醚(EGME)、冰醋酸(AA)以及AA/EGME作为复合添加剂,采用干-湿相转化技术制备了中空纤维非对称纳滤膜,重点考察了非溶剂添加剂对中空纤维膜结构和性能的影响。结果表明非溶剂添加剂的加入导致了中空纤维膜孔结构由指状转变为海绵状,从而引起中空纤维膜性能的变化。当聚合物质量分数为23%,铸膜液溶剂体系为m(AA)∶m(EGME)∶m(NMP)=5.7∶16.5∶54.8时,中空纤维膜对PEG600的截留率高于96%,纯水通量为211 L/(m2.h)。     

Isotactic polypropylene hollow microfibers prepared by CO2 laser‐thinning

An isotactic polypropylene hollow microfiber was continuously produced by using a carbon dioxide (CO₂) laser‐thinning method. To prepare the hollow microfiber continuously, the apparatus used for the thinning of the solid fiber was improved so that the laser can circularly irradiate to the hollow fiber. Original hollow fiber with an outside diameter (OD) of 450 μm and an internal diameter (ID) of 250 μm was spun by using a melt spinning machine with a specially designed spinneret to produce the hollow fiber. An as‐spun hollow fiber was laser‐heated under various conditions, and the OD and the ID decreased with increasing the winding speed. For example, when the hollow microfiber obtained by irradiating the CO₂ laser to the original hollow fiber supplied at 0.30 m min^?1 was wound up at 800 m min^?1, the obtained hollow microfiber had an OD of 6.3 μm and an ID of 2.2 μm. The draw ratio calculated from the supplying and the winding speeds was 2667‐fold. The hollow microfibers obtained under various conditions had the hollowness in the range of 20–30%. The wide‐angle X‐ray diffraction patterns of the hollow microfibers showed the existence of the highly oriented crystallites. Further, the OD and ID decreased, and the hollowness increased by drawing hollow microfiber obtained with the laser‐thinning. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2600–2607, 2006     

表面修饰聚乙烯亚胺的壳聚糖微球对十二烷基苯磺酸钠的吸附特性

采用乳化交联法制备交联壳聚糖微球(CCS),在其表面接枝聚乙烯亚胺(PEI),得到系列具有不同离子交换容量(IEC)的PEI修饰交联壳聚糖微球(PEI-CCS),对其进行表征,考察了其对十二烷基苯磺酸钠(SDBS)的静态吸附特性. 结果表明,PEI-CCS平均粒径为85 mm,IEC最高达1275 mmol/g,远高于CCS的418 mmol/g. 酸性条件下,PEI-CCS的胺基质子化,带正电荷,能与溶液中的阴离子吸附结合,对SDBS有良好的吸附能力. 吸附过程自发放热,可用准二级动力学模型和Langmuir吸附等温模型描述. PEI-CCS对SDBS的最大吸附量随IEC增加而增大,IEC=1275 mmol/g的PEI-CCS的最大吸附量为1487.61 mg/g,是CCS最大吸附量(510.20 mg/g)的2.92倍,吸附-脱附7次循环后,吸附量下降17.8%. PEI-CCS具有良好的重复使用性.     

Poly(ethyleneimine) infused and functionalized Torlon-silica hollow fiber sorbents for post-combustion CO2 capture

Organic–inorganic hybrid materials functionalized with amine-containing reagents are emerging as an important class of materials for capturing carbon dioxide from flue gas. Polymeric silica hollow fiber sorbents are fabricated through the proven dry-jet/wet-quench spinning process. In our study, a new technique for functionalizing polymeric silica hollow fiber sorbents with poly(ethyleneimine), followed by a post-spinning infusion step was studied. This two step process introduces a sufficient amount of poly(ethyleneimine) to the polymeric silica hybrid material support to improve the CO₂ sorption capacity due to the added amine groups. The poly(ethyleneimine) infused and functionalized hollow fiber sorbents are also characterized by a thermal gravimetric analyzer (TGA) to assess their CO₂ sorption capacities.     

Preparation and adsorption properties of poly(N‐vinylformamide/acrylonitrile) chelating fiber for heavy metal ions

In this article we report a new chelating fiber that was prepared from a hydrolyzate of poly(N‐vinylformamide/acrylonitrile) by a wet‐spinning method. This fiber contains chelating groups, such as amidine groups, amino groups, cyano groups, and amide groups, with high densities. We examined the chelating abilities for several metal ions with this fiber, and present the morphological merit of the fibrous product compared with the globular resin. Based on the research results, it is shown that the fiber has higher binding capacities and better adsorption properties for heavy metal ions than the resin. The pH value of the metal ion solution shows strong influences on the adsorption of the metal ions. The maximum adsorption capacities of the fiber for Cu²⁺, Cr³⁺, Co²⁺, Ni²⁺, and Mn²⁺ are 112.23, 88.11, 141.04, 108.06, and 73.51 mg/g, respectively. In mixed metal ions solution, the fiber adsorbs Cr³⁺, Cu²⁺ and Co²⁺ efficiently. The adsorbed metal ions can be quantitatively eluted by hydrochloric acid. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1378–1386, 2002     

聚醚砜中空纤维膜的成形条件与形态结构研究

采用扫描电镜探讨经双向拉伸聚醚砜(PES)中空纤维膜的纺制工艺条件与结构之间的关系。在膜的中部通入填充液,随着填充液压力的增大,中空纤维膜的壁厚明显减小,同时纤维膜表面的孔明显增多。随着凝固浴质量分数的增加,中空纤维膜表面的孔径先减小后增大,而中空纤维膜接近外表面的皮层逐渐变厚。随着凝固浴拉伸率的提高,中空纤维膜在外径不变的情况下壁厚减小,内表面积增加;纤维变薄而且更为致密。     

Pore structure and properties of poly(ether ether ketone) hollow fiber membranes: influence of solvent‐induced crystallization during extraction

Poly(ether ether ketone) (PEEK) hollow fiber membranes were prepared by a thermally induced phase separation method with polyetherimide as diluent, and N‐methyl pyrrolidone (NMP), dichloromethane and a composite extractant composed of NMP, ethanolamine and water as extractant. The effects of the different solvents induced crystallization on the pore structure during extraction and the properties of the PEEK hollow fiber membranes were investigated in detail. The crystallization behaviors of the membranes were characterized by DSC and XRD. The effect of the extractants on the microscopic morphologies, pore structures, water fluxes and mechanical properties of the membranes were investigated. The results showed that the extraction ability of the composite extractant was the most significant, followed by NMP and dichloromethane. The crystallinity of the hollow fiber was 39.0% before extraction and was elevated to 39.2% after the extraction with NMP, 46.6% with dichloromethane and 46.7% with the composite extractant, which shows that dichloromethane and the composite extractant have strong ability to induce the crystallization of PEEK. The inner and outer surfaces of the membranes obtained after extraction by the composite extractant had the largest pore size and the highest surface porosity. The most probable pore diameter of the membranes obtained after extraction by NMP, dichloromethane and the composite extractant was 23.26 nm, 24.43 nm and 24.43 nm, respectively, which indicated that solvent‐induced crystallization was beneficial for the formation of larger pores. The pure water flux of the PEEK membrane prepared by the composite extractant was the largest, but the tensile strength was the lowest. © 2019 Society of Chemical Industry     

Selective reduction of aromatic nitro compounds over recyclable hollow fiber membrane‐supported Au nanoparticles

Guanidylated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (GPPO) hollow fiber membrane (HFM) supported Au nanoparticles are prepared by a simple adsorption‐reduction of Au³⁺ with sodium borohydride as a reducing agent and polyvinyl pyrrolidone as a dispersant. The novel heterogeneous catalyst shows high catalytic activity for the reduction of various aromatic nitro compounds in an aqueous medium at room temperature and can be easily reused for several runs, for example, for the reduction of nitrobenzene, the yield reaches up to 92% even after 10 cycles, indicating the potential application of GPPO HFM as a catalysts support material for sustainable chemistry. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41268     

Absorbency and adsorption of poly(acrylic acid‐co‐acrylamide) hydrogel

Poly(acrylic acid‐co‐acrylamide) (PAAAM) hydrogels have been prepared from partly neutralized acrylic acid (AA) and acrylamide (AM) by solution polymerization, and their absorbency and adsorption in both CuCl₂ and FeCl₃ solutions have been investigated. PAAAM hydrogels and their complexes with Cu²⁺ or Fe³⁺ have been characterized by FTIR. The absorbency of PAAAM in both CuCl₂ and FeCl₃ solutions increases initially and then decreases as the absorbing time increases. The adsorption of PAAAM in both CuCl₂ and FeCl₃ solutions can be described by the pseudo‐second order chemisorption kinetics proposed by Ho and McKay, and the equilibrium uptake of Cu²⁺ on PAAAM can well be fit with the Langmuir adsorption isotherm. However, the equilibrium uptake of Fe³⁺ on PAAAM increases as the initial Fe³⁺ concentration increases for Fe³⁺ concentration smaller than 5.625 × 10^?3 mol/L, and then decreases with Fe³⁺ concentration. The largest uptakes for Cu²⁺ and Fe³⁺ are 247 and 173 mg/g, respectively. The results also show that the uptake of Cu²⁺ and Fe³⁺ on PAAAM increases remarkably when pH of the solution is changed from 2.3 to 4.2 and from 1.0 and 2.1, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Crystal structure of poly(ethylenimine)-hydrogen chloride complex

Linear poly(ethylenimine) was found to form a crystalline complex with hydrogen chloride when poly(ethylenimine) in the state of its anhydrate or hydrates was immersed in concentrated hydrochloric acid or exposed to HCl vapour. The crystal structure of the HCl complex was determined by X-ray diffraction. The crystals are metrically tetragonal with cell constants a = B = 5.06 Å and c (chain axis) = 7.57 Å and the unit cell includes one planar zigzag polymer chain (two monomeric units) and two HCl molecules (the molar ratio is 1:1). The space group of the crystals is, however, not of the tetragonal system: the structure determined can be expressed in terms of any of the following crystal systems and space groups: orthorhombic P222₁, orthorhombic Pcm2₁, orthorhombic Pc2m, and monoclinic P2₁/m (c unique). The Cl···N distance of 3.05 Å strongly indicates that every NH and HCl hydrogen atom participates in hydrogen bondings between nitrogen and chlorine atoms. The HCl complex has a fairly high melting temperature of 265°C, which is about 200°C higher than those of the anhydrate and hydrates.     

Hydrophilic modification of poly(vinylidene fluoride) membrane with poly(vinyl pyrrolidone) via a cross‐linking reaction

A highly hydrophilic hollow fiber poly(vinylidene fluoride) (PVDF) membrane [PVDF‐cl‐poly(vinyl pyrrolidone) (PVP) membrane] was prepared by a cross‐linking reaction with the hydrophilic PVP, which was immobilized firmly on the outer surface and cross‐section of the PVDF hollow fiber membrane via a simple immersion process. The cross‐linking between PVDF and PVP was firstly verified via nuclear magnetic resonance measurement on PVP solution after cross‐linking. The hydrophilic stability of the modified PVDF membrane was evaluated by measuring the pure water flux after different times of immersion and drying. The anti‐fouling properties were estimated by cyclic filtration of protein solution. When the cross‐linking time was as long as 6 hr and the PVP content reached 5 wt %, the pure water flux (J_v) was constant as ～ 600 L m^?2 hr^?1. The hydrophilicity of the PVDF‐cl‐PVP membrane was significantly enhanced and exhibited a good stability. The PVDF‐cl‐PVP membrane showed an excellent anti‐protein‐fouling performance during the cyclic filtration of bovine serum albumin solution. Therefore, a highly hydrophilic and anti‐protein‐fouling PVDF hollow fiber membrane with a long‐term stability can be prepared by a simple and economical cross‐linking process with PVP. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and performances of poly(phthalazinone ether sulfone ketone) hollow fiber membranes with excellent thermotolerance

The cloud points of PPESK/NMP/H₂O ternary system at different temperatures were measured by titrimetric method. The binodal lines in the ternary phase diagram of the poly(phthalazinone ether sulfone ketone (PPESK) dope system was determined, on the basis of the cloud point experimental data being linearly fitted with the semiempirical linear cloud point correlation. Furthermore, phase separation behavior during the phase inversion of PPESK membrane‐forming system was discussed in terms of the phase diagram. Then, dry–wet spinning technique was employed in manufacturing PPESK hollow fiber membranes by immersion precipitation method. The cross‐section morphologies of hollow fibers were observed by scanning electronic microscopy. Also, the effects of dope solution composition and spinning parameters, including the coagulant composition and the spinning temperature on the separation performances of fibers, were evaluated by permeability measurements. The thermotolerance of the PPESK hollow fiber membranes prepared in the work was examined for the permeation operation at different temperatures and pressure differences. The experimental results showed that pure water flux increases several fold along with the temperature increases from 20 to 80°C at different operation pressures, while the solute rejection only decreases slightly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 878–884, 2006     

Adsorption of heavy‐metal ions on poly(ethylene imine)‐immobilized poly(methyl methacrylate) microspheres

Poly(methyl methacrylate) (PMMA) microspheres carrying poly(ethylene imine) (PEI) were prepared for the removal of heavy‐metal ions (copper, cadmium, and lead) from aqueous solutions with different amounts of these ions (50–600 mg/L) and different pH values (3.0–7.0). Ester groups in the PMMA structures were converted to imine groups in a reaction with PEI as a metal‐chelating ligand in the presence of NaH. The adsorption of heavy‐metal ions on the unmodified PMMA microspheres was very low [3.6 μmol/g for Cu(II), 4.6 μmol/g for Cd(II), and 4.2 μmol/g for Pb(II)]. PEI immobilization significantly increased the heavy‐metal adsorption [0.224 mmol/g for Cu(II), 0.276 mmol/g for Cd(II), and 0.126 mmol/g for Pb(II)]. The affinity order of adsorption (in moles) was Cd(II) > Cu(II) > Pb(II). The adsorption of heavy‐metal ions increased with increasing pH and reached a plateau value around pH 5.5. Their adsorption behavior was approximately described with the Langmuir equation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 197–205, 2001     

Electrochemical impedance study of self-assembled layer-by-layer iron–silicotungstate/poly(ethylenimine) modified electrodes

Electrochemical impedance spectroscopy (EIS) has been used to study multilayer films containing anionic iron-substituted silicotungstate [SiW₁₁Fe^III(H₂O)O₃₉]⁵⁻ (SiW₁₁Fe) and positively charged poly(ethylenimine) self-assembled by the layer-by-layer method on glassy carbon and indium tin oxide electrodes. The effect of the charge of the outermost layer of the multilayer assembly on the electron transfer of soluble species was studied using the redox probes [Fe(CN)₆]³⁻ and [Ru(NH₃)₆]³⁺; cyclic voltammetry indicating that the surface charge has a significant effect on the process. EIS demonstrated that the electrostatic attraction or repulsion between the surface and the redox probes plays a significant role. Analysis of the impedance spectra showed that the charge transfer resistance increases with an increasing number of bilayers for both redox probes and that the porosity of the multilayer film, which varies with the electrode substrate, also has a significant effect on the electrochemical response.     

丙烯酸酯/苯乙烯共聚物中空微球对聚硫密封剂性能的影响

以丙烯酸酯/苯乙烯共聚物中空微球作为聚硫密封剂的填料,考查微球性能和用量对密封剂性能的影响。试验结果表明,微球形貌规整,具有良好的耐热性。随着微球用量的增加,聚硫密封剂密度降低,黏度增大,室温硫化后拉伸强度、断裂伸长率和硬度均增大,耐热空气老化后拉伸性能也有增大趋势。