Studies on hydrophilic polysulfone ultrafiltration membranes

Ultrafiltration membranes were produced from carboxylated polysulfone polymers having different degrees of substitution (DS). Solute separation was found to increase with increasing DS. The techniques of single solute permeation and permoporometry were used to determine the pore size of these membranes. Permoporometry measurements indicated that pore size decreased with increasing DS. Solute separation was predicted by inserting the distribution of pore sizes obtained from permoporometry into a restricted transport model. Similar results were obtained from a nonlinear least squares fit of the restricted transport model to the experimental data. Both techniques produced similar sieving curves. It was concluded that pore size decreases were not due to the increasing repulsion of solute molecules by hydrophilic polysulfone but to changes in polymer solution properties as the DS increased.     

聚偏氟乙烯膜亲水改性研究进展

聚偏氟乙烯以其优异的力学性能和化学性能被广泛用于制备微滤膜、超滤膜、纳滤膜和反渗透膜等水处理膜材料,然而由于其极强的疏水性,使其在用于水处理过程中存在通量低和容易被污染等缺陷,这极大地降低了水处理效率和薄膜的使用寿命,因此对其亲水改性具有重要的实际意义。本文根据改性方法的异同,将近几年来国内外对聚偏氟乙烯膜的亲水化改性研究工作按共混改性、共聚改性、表面接枝改性和表面涂覆改性等方法进行了综述,通过不同改性方法对聚偏氟乙烯水处理膜的亲水效果、渗透能力和防污染性等方面的影响,着重比较讨论了各种改性方法的改性效果及优缺点。最后对未来聚偏氟乙烯膜的亲水改性研究及工业化应用的发展趋势进行了展望。     

聚偏氟乙烯超滤膜亲水改性研究进展

膜污染会缩短超滤膜的使用寿命,增加由于水力清洗、化学清洗以及膜组件更换而产生的费用。为减少运行成本,有必要对膜污染加以控制。膜污染与原水中污染物的性质和膜本身的性质密切相关。亲水性膜具有水通量高、抗污染性能好的特点,因而提高超滤膜的亲水性是提高膜的水通量和控制膜污染的重要方法之一。简要介绍了具有良好化学稳定性、耐辐射性、耐热性的聚偏氟乙烯膜的表面亲水改性和共混亲水改性的研究进展,指出通过不同的改性方式,聚偏氟乙烯膜都能够实现亲水性的增强。     

Gas permeability and permselectivity of plasma‐treated polypropylene membranes

The effects of NH₃‐plasma and N₂‐plasma treatment on rubbery polypropylene (PP) membrane upon permeation behavior for CO₂, O₂, and N₂ were investigated from their permeability measurements. The NH₃‐plasma and N₂‐plasma treatment on PP membranes could increase both the permeability coefficient for CO₂ and the ideal separation factor for CO₂ relative to N₂. For O₂ transport, both the permeability coefficient for O₂ and the ideal separation factor for O₂ relative to N₂ also increased. NH₃‐plasma and N₂‐plasma treatment on PP membranes possibly brings about an augmentation of permeability for CO₂ and permselectivity of CO₂ relative to N₂ simultaneously, but unfortunately the plasma‐treated PP membrane does not reach the level of CO₂ separation membrane. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

铝合金表面亲水膜层研究

以硅酸钠、乙酸乙酯、聚丙烯酰胺等为主要成分制备出亲水膜层。测定了该亲水膜层涂覆在铝合金表面的亲水性、耐蚀性和耐热性等。结果表明：其亲水性、耐蚀性和耐热性优良，能满足空调铝合金翅片的使用要求。     

Simultaneous enhancements of mechanical properties and hydrophilic properties of polypropylene via nano‐silicon dioxide modified by polydopamine

This study is focused on the development of high‐performance composite materials based on nano silicon dioxide (nano‐SiO₂) modified by polydopamine (PDA). A facile one‐step method was developed to synthesize core–shell structured SiO₂@polydopamine (PDA) nanospheres. During the synthesis, a PDA shell was simultaneously coated on the SiO₂ nanospheres to form the core–shell nanostructure which was blended with polypropylene (PP) and β nucleating agent (β‐NA) to enhance both mechanical and hydrophilic properties. Nano‐SiO₂ particles modified by PDA (SiO₂@polydopamine) influence the crystallization of PP seriously. The results indicated that when 1%wt SiO₂@polydopamine was added, the impact strength of composite reached the maximum value 12.60k J/m² increasing 137% compared with PP, the bending strength and bending modulus decreased slightly reaching 41.85 MPa, and 2192 MPa, respectively, the composite possessed hydrophilic performance with the water contact angle of 88.32°. β nucleating agent was used in all formulations, the synergistic effect toward mechanical properties with SiO₂@polydopamine was studied. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45004.     

高亲水膜-聚乙烯醇复合膜的研究进展

PVA复合膜是将亲水性的PVA皮层材料负载于支撑体上形成的。本文对PVA复合膜在不同领域（RO、UF、MF）中的应用研究进展以及改性PVA复合膜的研究情况进行了综述,并对将来的研究方向提出了展望。     

聚丙烯微孔膜的研究进展

介绍了由熔融纺丝-冷却拉伸法和热致相分离法制备聚丙烯微孔膜的原理和过程。对当前膜研究领域的热点即膜的亲水化改性研究进行了重点评述,包括暂时性改性和永久性改性。阐述了各种改性方法的特点,着重讨论了亲水化改性对膜性能如膜的微孔孔径、孔隙率、透水量等的影响,强调膜表面亲水性的提高可改善膜的耐生物污染性。指出聚丙烯微孔膜的应用领域和发展前景。     

Modelling of the pervaporative flux through hydrophilic membranes

This work presents a simplified model of wide applicability for the determination of the pervaporation flux through hydrophilic membranes, provided that the adsorption isotherm of the permeating species onto the pervaporation membrane has a linear shape. The model predicts the pervaporation flux as a function of the activity of the penetrant in the liquid phase and the operation temperature. Experimental results obtained working with two polymeric membranes (CMC‐CF‐23 and Pervap 2256) applied to the dehydration of tetrahydrofuran (THF) and to the separation of methanol from alcohol–ether mixtures, respectively, have been satisfactorily correlated and the characterising parameters have been obtained. Furthermore, the model has been also tested against results obtained with two ceramic membranes, Pervap SMS and zeolite NaA, applied to the dehydration of ketonic mixtures and of tetrahydrofuran respectively. Copyright © 2005 Society of Chemical Industry     

Tannic acid coating and in situ deposition of silver nanoparticles to improve the antifouling properties of an ultrafiltration membrane

The construction of antifouling membranes has been a desirable approach for addressing membrane-fouling issues in the ultrafiltration (UF) process. Antifouling means antiadhesive and antimicrobial; however, few researchers have achieved both properties in a facile and effective manner. In this article, we report a direct tannic acid (TA) coating method combined with the in situ deposition of silver nanoparticles (Ag NPs); this was used to improve the antifouling properties of a positively charged polymeric UF membrane. The results show that the TA–Ag NP modified membranes showed improved protein resistance (flux recovery rate = 71.2% after modification vs 17.8% before modification) and less attachment of bacteria (Escherichia coli K1) on the membrane surface and reduced cell viability in the resulting bacterial suspension (reduced by ≥90%) because of the combined antimicrobial properties of both the TA and Ag NPs. This indicated that our modification method was promising for UF membrane antifouling applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47314.     

Preparation of soluble polyimides and ultrafiltration membrane performances

Various soluble polyimides with bis[4‐(3‐aminophenoxy)phenyl]sulfone and three kinds of dianhydrides were prepared in a polar N‐methyl‐2‐pyrrolidone solvent by the traditional chemical two‐step method. All the polymers synthesized had good solubilities in polar solvents and excellent thermal properties. Wide‐angle X‐ray diffraction studies showed that all polyimides were amorphous. Polyimide ultrafiltration asymmetric membranes were successfully prepared by the traditional phase‐inversion method. The cross sections of the polyimide ultrafiltration membranes showed a very thin surface layer and a porous sublayer. The pure water flux was very high and the solute rejection rate at poly(ethylene glycol) of MW 20,000 was above 90%. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1–9, 2000     

亲水化改性PVDF超滤膜的抗污染特性研究

以不同通量的自制亲水化纳米SiO2改性PVDF超滤膜(PS)和聚乙烯醇改性PVDF超滤膜(PA),对城市污水二级出水(EfOM)和牛血清蛋白(BSA)水溶液进行了过滤试验,通过对比未添加改性剂的PVDF超滤膜,考察通量衰减率、膜污染阻力构成、通量恢复率等指标,分析水质与膜材料间的相互关系对超滤膜抗污染能力的影响.结果表明,在BSA料液中,3种通量下,低通量的膜抗污染能力好于高通量膜.20 min内PA膜表现出最低的膜通量衰减,而P膜在过滤初期通量就急剧下降.在EfOM料液中,各通量下,P膜通量衰减严重且产生了不可逆的堵孔阻力,亲水化改性后膜通量衰减率降低,稳态通量高,膜污染阻力主要来自于浓差极化和滤饼层阻力,其中PS膜通量下降率最低,而PA膜清洗后通量易恢复.     

Characterization and comparative evaluation of polysulfone and polypropylene hollow fiber membranes for blood oxygenators

Blood oxygenators are used to saturate oxygen levels and remove carbon dioxide from the body during cardiopulmonary bypass. Although the natural lung is hydrophilic, commercially used oxygenator materials are hydrophobic. Surface hydrophobicity weakens blood compatibility, as long-term contact with the blood environment may lead to different degrees of blood activity. Polysulfone may be considered an alternative hydrophilic material in the design of oxygenators. Therefore, it may be directed toward developing hydrophilic membranes. This study aims to investigate the feasibility of achieving blood gas transfer with a polysulfone-based microporous hollow fiber membrane and compare it with the commercially available polypropylene membranes. Structural differences in the membrane morphology, surface hydrophilicity, tortuosity, mass transfer rate, and material properties under different operation conditions of temperature and flow rates are reported. The polysulfone membrane has a water contact angle of 81.3°, whereas a commercial polypropylene membrane is 94.5°. The mass transfer resistances (s/m) for the polysulfone and polypropylene membranes are calculated to be 4.8 × 10⁴ and 1.5 × 10⁴ at 25°C, respectively. The module made of polysulfone was placed in the cardiopulmonary bypass circuit in parallel with the commercial oxygenator, and pH, pO₂, pCO₂ levels, and metabolic activity were measured in blood samples.     

Syndiotactic polypropylene as potential material for the preparation of porous membranes via thermally induced phase separation (TIPS) process

This work reports the flat sheet membrane preparation from syndiotactic polypropylene (sPP) by thermally induced phase separation (TIPS) process. sPP obtained by polymerization using metallocene catalysts and isotactic polypropylene (iPP) also obtained via metallocene catalysis with similar molecular weight were used. The phase diagrams of sPP and iPP with diphenylether as diluent were obtained. The properties of three representative membranes from sPP and three from iPP, prepared using different PP concentrations were evaluated with respect to membrane pore structure, gas flow, liquid displacement (bubble point), and water permeability. Two selected membranes, one from sPP and one from iPP were analysed with regard to polypropylene bulk morphology (X-ray diffraction) and mechanical properties (tensile strength). Under the same formation conditions, membranes with less inter-connected pores and less porous surface were obtained from sPP compared with iPP. Overall, lower permeabilities had been found for the sPP membranes, which were attributed to the difference in pore morphology. The differences between sPP and iPP were also discussed in terms of different driving forces for liquid-liquid demixing as deduced from the phase diagrams. The X-ray analysis had shown that the sPP membranes had a higher amorphous phase content than that in iPP, and the mechanical test had revealed a pronounced ductile behaviour for sPP samples. These results helped to explain the lower permeabilities of the sPP membranes, and their pressure-dependency.     

Surface modification of polypropylene membrane by low‐temperature plasma treatment

Microporous polypropylene membranes were low temperature plasma treated with acrylic acid and allylamine. Parameters of plasma treatment were examined and optimized for the enhancement of membrane performance properties. Excess power damaged the membrane surface and excess monomer flow rate increased the reactor pressure to interfere with the glow discharge. Longer plasma treatment time resulted in even more plasma coating and micropore blocking. The contact angle with water decreased and wettabilities increased with the increase of plasma treatment time. Deposition of the plasma polymer on the membrane surface was confirmed by FTIR/ATR spectra of the treated surface. In determining the flux, the hydrophilicity of the surface played a role as important as that of the micropore size. Adequate plasma treatment could enhance both water flux and solute removal efficiency. Results from the BSA (bovine serum albumin) solution test confirmed that fouling was greatly reduced after the plasma treatment. The BSA solution flux through the plasma‐treated membranes depended on pH, whereas pH variation had no serious effects on the untreated membrane. Modification of the surface charge by the plasma treatment should exert a substantial influence on the adsorption and removal of BSA. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1555–1566, 2001     

Facile fabrication of polyester filament fabric with highly and durable hydrophilic surface by microwave‐assisted glycolysis

Poly(ethylene terephthalate) (PET) fabric with highly and durable hydrophilic surface was fabricated using microwave‐assisted glycolysis. Sodium hydroxide (NaOH) as a catalyst was proven to be suitable for PET glycolysis under assistance of microwave. The modified PET fabric (0.5% NaOH, irradiation 120 s) showed high surface hydrophilicity with a contact angle of 17.4 ° and a wicking length of 19.36 mm. The exposure of the carboxyl‐ and hydroxyl‐end groups on the surface of PET and the introduction of etches were confirmed by Methylene Blue staining and field emission scanning electron microscopy (FESEM), receptively. Although the strength of PET fabric decreased after modification, it was still high enough for textile applications. The thermal properties of the modified PET fabrics were well maintained. The high hydrophilicity and its original properties of PET could be controlled by changing the irradiation time from 60 s to 120 s and adjusting the content of sodium hydroxide from 0.2% to 0.5%. These results suggest microwave‐assisted glycolysis with sodium hydroxide is an effective method for PET hydrophilic finishing. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44069.     

Polydopamine hydrophilic modification of polypropylene separator for lithium ion battery

The modified polypropylene (PP) separators with self‐polymerization of dopamine on the surfaces are prepared by a simple solution‐immersion method to improve the interfacial hydrophilic and discharge performance. The contact angle test and the liquid electrolyte uptake capacity test results show that the wettability and the electrolyte‐retention ability of polydopamine‐modified separator are improved significantly. The robust and thin polydopamine layer on the surface also enhances thermal performance and tensile strength of the modified PP separator certified by DSC and tensile strength tests. The ionic conductivity of the modified PP separator is up to 3.08 mS·cm^?1, ～2.5 times of the bare separator. Good discharge capacity retention and C‐rate discharge performance are demonstrated by a 2025 coin half‐cell with the liquid electrolyte‐soaked polydopamine modified PP separator sandwiched between lithium metal anode and LiFePO₄ cathode. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40543.     

聚偏氟乙烯膜亲水化改性研究进展

为弥补强疏水性聚偏氟乙烯(PVDF)膜在实际应用中的缺陷,从膜本体及膜表面2个角度入手,阐述了国内外对PVDF膜亲水化改性的主要方法。膜本体改性主要是将膜材料与亲水性聚合物或无机纳米材料共混,从而改善PVDF膜的亲水性能;而膜表面改性则主要是通过表面涂覆改性与表面接枝改性来实现。PVDF膜亲水性的增强,能有效改善膜的抗污染能力,从而大大提高膜的过水通量,并延长其使用寿命。     

Continuous Application of Polyglycerol‐Supported Salen in a Membrane Reactor: Asymmetric Epoxidation of 6‐Cyano‐2,2‐dimethylchromene

In the current work, suitability of hyperbranched polyglycerol as a high loading catalyst support is demonstrated. A polyglycerol‐supported manganese‐salen complex (chemzyme) is applied as a homogeneous catalyst in the epoxidation of 6‐cyano‐2,2‐dimethylchromene. The recyclability of the corresponding catalyst was investigated in repetitive batch experiments as well as a continuous operation of the reaction in an ultrafiltration membrane reactor. An enhanced stability of the catalyst in repetitive batches was observed as a result of immobilization whereby the total turnover number increased from 23 in a single batch to 80 in four repetitive batches. To enable continuous operation, a continuously operated, stirred tanked reactor (CSTR) was equipped with an ultrafiltration membrane (MPF‐50) and a retention of 98% was determined. The continuous chemzyme membrane reactor was operated over the course of 20 residence times. After approximately 12 residence times, the steady state was reached yielding 70% conversion as well as an enantiomeric excess up to 92%. A space‐time yield (sty) of 458 g L ⁻¹ d⁻¹ and a turnover frequency (TOF_reaction) of up to 18 h⁻¹ was reached in the steady state. It was determined that the total turnover number (TTN) was enhanced by a factor of 10 from 24 (batch) up to 240 for 20 residence times in CSTR operation.     

Polypropylene/polypropylene‐grafted acrylic acid copolymer/ethylene–Acrylic acid copolymer ternary blends for hydrophilic polypropylene

Ternary blends of polypropylene (PP), a polypropylene‐grafted acrylic acid copolymer (PP‐g‐AA), and an ethylene–acrylic acid copolymer (EAA) were prepared by melt blending. The surfaces of films with different contents of these three components were characterized with contact‐angle measurements. Scanning electron microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis were used to characterize the microstructure, melting and crystalline behavior, and thermal stability of the blends. The contact angles of the PP/PP‐g‐AA blends decreased monotonically with increasing PP‐g‐AA content. With the incorporation of EAA, the contact angles of the PP/PP‐g‐AA/EAA ternary blends decreased with increasing EAA content. When the concentration of EAA was higher than 15 wt %, the contact angles of the ternary blends began to increase. Scanning electron microscopy observations confirmed that PP‐g‐AA acted as a compatibilizer and improved the compatibility between PP and EAA in the ternary blends. Differential scanning calorimetry analysis suggested that acrylic acid moieties could act as nucleating agents for PP in the polymer blends. Thermogravimetric analysis and differential thermogravimetry confirmed the optimal blend ratio for the PP/PP‐g‐AA/EAA ternary blends was 70/15/15. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 436–442, 2006