新型含钴硅橡胶离聚体膜的富氧性能

硅橡胶 ( PDMS)是最早使用的气体分离膜材料 ,其氧透过系数较高 ( PO2 =6 0 0 Barrer) ,但氧氮分离系数低 ( αO2 /N2 =2 .0 ) ,成膜性及膜强度差 ,因而限制了其应用 .PDMS改性一直是气体分离膜研究的重要课题[1] ,提高氧氮分离性 ,改善成膜性 ,而不影响其透气性 ,成为人们追求     

Facilitated Transport of Molecular Oxygen in Membranes of Macromolecular Cobalt-Porphyrin Complex: Modification of Dual-Mode Transport Model

Transport of molecular oxygen is facilitated in poly(butyl methacrylate) membranes containing the cobalt(II)-α,α′,α″,α′″-meso-tetrakis(o-pivalamidophenyl)porphyrin-1-methylimidazole (CoPIm) complex which forms oxygen adduct rapidly and reversibly. The facilitated transport of oxygen is studied by modifying a dual-mode transport model for gas permeation. The diffusion coefficient of oxygen via the fixed CoPIm complexes (Langmuir mode) is assumed to depend on oxygen concentration, and the modified dual-mode transport equation is described for the permeation steady state. The modified equation represents the effect of upstream oxygen pressure on the permeability. The oxygen permeation behavior through the macromolecular-metal complex membrane is discussed.     

Facilitated transport of molecular oxygen in cobaltporphyrin/poly(1-trimethylsilyl-1-propyne) membrane

The combination membrane of poly(1-trimethylsilyl-1-propyne) with enormously high permeability and poly(vinylimidazole)-bound porphinatocobalt with selective oxygenbinding ability was prepared. Oxygen transport through the membrane was facilitated in terms of oxygen transport via the latter domain as a fixed oxygen-carrier, and this oxygen permeability maintained for a month.     

Etching of polyethylene terephthalate thin films by neutral oxygen atoms in the late flowing afterglow of oxygen plasma

Films of polyethylene terephthalate were deposited on quartz crystals and exposed to oxygen atoms to study their etching characteristics and quantify the etching rate. Oxygen (O) atoms were created by passing molecular oxygen through plasma created in a microwave discharge. The discharge power was fixed at 250 W, while the pressure of oxygen was 50 Pa. Before exposure to oxygen atoms, a thin polymer film of polyethylene terephthalate (PET) was deposited uniformly over a crystal with a diameter of 12 mm. The crystal was mounted on a quartz crystal microbalance to accurately determine the thickness of the polymer film. The polymer film was exposed to O atoms in the flowing afterglow. The density of O atoms was measured with a cobalt catalytic probe mounted next to the sample and was determined to be 1.2 × 10²¹ m^–3. Samples were treated with O atoms for different periods of up to 120 min. The thickness of the film decreased linearly with treatment time. After 90 min of treatment, a 65‐nm‐thick polymer film was completely removed. Therefore, the etching rate was 0.5 nm/min, so the interaction probability between an O atom and an atom in the sample was extremely low, just 1.4 × 10^–6. Samples treated for different periods were investigated by atomic force microscopy and X‐ray photoelectron spectroscopy to examine the etching characteristics of O atoms in the flowing afterglow. Copyright © 2012 John Wiley & Sons, Ltd.     

O2/n2-separation by polymer-bound cobalt complexes

Facilitated or complexation-mediated transport of oxygen in the solid membrane containing a fixed carrier was described, by using the polymer-bound cobalt Schiff's base chelate (CoS) and cobaltporphyrin (CoP). α³ β-Substituted cobaltporphyrin derivatives were synthesized: The oxygen-binding reaction to cobalt was affected by the cavity structure on porphyrin, i.e., unbulky amido-substituted groups such as acetylamido- and acrylamido-substituents enhanced oxygen-binding and -dissociation rate constant or provided an oxygen-binding pathway. Oxygen transport through the membranes of these polymer-bound CoP derivatives was selectively augmented due to the rapid and reversible oxygen-binding. Diffusion constants via the fixed CoPs correlated to the characteristics of oxygen-binding reaction.     

氟涂层对聚合物-钴卟啉膜氧气输送性能及其寿命的影响

采用在聚合物-钴卟啉(CoP)膜表面旋转涂覆氟涂料法,制备了氧/氮分离膜.研究表明,与未涂层膜相比,氟涂层膜中的CoP与氧表观结合平衡常数、膜的氧渗透系数和氧/氮选择性没有发生明显变化.随氟涂层厚度增加,氧渗透系数稍有降低,但水蒸汽渗透系数显著降低.由于氟涂层的憎水性,使涂层膜的水蒸汽渗透系数显著降低,氧载体CoP与氧结合寿命延长了4倍.     

氧在甲基丙烯酸辛酯-乙烯基咪唑共聚物/钴卟啉复合膜中的溶解和扩散过程

讨论了氧在甲基丙烯酸辛酯 乙烯基咪唑共聚物 钴卟啉复合膜中的溶解和扩散过程,用二元输送模型分析了间α,α,α,α-四(邻三甲基乙酰胺苯基)钴卟啉(CoP)作为氧载体的复合膜氧输送性能.研究发现,固定在聚合物中的CoP与氧可逆地络合和解络合,其络合平衡常数K为14mol- 1 L ,根据吸附实验结果计算出氧在基体聚合物中的物理溶解度系数kD 为4 4×10 - 5cm3(STP)cm- 3Pa- 1 .聚合物 载体复合膜除了物理渗透外,氧还可通过与载体的络合和解络合而扩散,从而促进氧的输送.氧通过载体的扩散系数(DC)和通过基体聚合物的物理扩散系数(DD)的比值为0 0 8.     

Structural changes of silver polymer electrolytes: Comparison between poly(2‐ethyl‐2‐oxazoline) and poly(N‐vinyl pyrrolidone) complexes with silver salt

The difference between the polymer matrices of poly(2‐ethyl‐2‐oxazoline) (POZ) and poly(N‐vinyl pyrrolidone) (PVP) does not have a significant effect on the facilitated propylene transport and propylene solubility in 1:1 polymer/silver salt complex membranes, according to our previous work. In this article, its origin is investigated in terms of both microstructures of silver polymer electrolytes and the coordinative interaction of silver ion with polymer and with the counteranion. Initially different microstructures of POZ and PVP become similar to each other upon dissolving a large amount of silver salt, as evidenced by propane transport properties, specific volume, and Bragg d‐spacing. The dissolution of the silver salt in the polymer solvent strongly depends on the coordinative interaction between silver ion and carbonyl oxygen of POZ and PVP. Thus, the structural similarity upon dissolving silver salts in POZ and PVP is primarily determined by the coordinative interaction between silver ion and carbonyl oxygen, which was confirmed by theoretical structure calculation based on density functional theory and by IR and Raman spectroscopy. Therefore, facilitated olefin transport for silver polymer electrolyte membranes does not strongly depend on the polymeric matrix at high silver concentrations. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 232–237, 2004     

Specific oxygen-binding to a polymer-supported N,N-disalicylidenethylenediaminocobalt complex

A polymer membrane containing N,N-disalicylidenethylenediaminocobalt (Co(salen)) was prepared. The Co(salen) supported in the polymer not only worked as a reversible and specific oxygen-adsorbent but discontinuously bound oxygen at the atmospheric oxygen partial pressure of ca. 15 cmHg to give an on-off-like oxygen-binding curve. Oxygen permeation through the Co(salen) membrane was also augmented in the higher upstream oxygen pressure region, which was caused by the specific oxygen-binding to the Co(salen) fixed in the membrane.     

Synthesis of a nano‐sized chiral imprinted polymer and its use as an (S)‐atenolol carrier in the bulk liquid membrane

In this work, nanosized chiral imprinted polymers containing (S)‐atenolol ((S)‐ATN) selective sites were synthesized by using suspension polymerization in silicon oil. (S)‐ATN, methacrylic acid, and ethylene glycol dimethacrylate were used as enantiomerically pure template, functional monomer, and cross‐linker, respectively. The prepared chiral imprinted polymers were used as the carrier elements in a bulk liquid membrane (BLM). (S)‐ATN transport capability of the chiral imprinted polymers was compared with that of the nonimprinted polymer. It was shown that chiral imprinted polymers could transport (S)‐ATN through the BLM more effectively than (R)‐ATN, whereas no difference in the facilitated transport was observed between (R)‐ATN and (S)‐ATN when using nonimprinted polymer particles as the carrier element in the BLM. A kinetic model was proposed for the transportation of (S)‐ATN through the chiral imprinted polymers based BLM. It was found that the extraction of ATN from the source to the membrane controls the chiral separation process. It was also found that the pH of source and receiving phases as well as the racemic ATN concentration in source phase had very crucial effect on the chiral separation efficiency.     

钴离子在P507为载体的支撑液膜中的传输

本文用国内的膜材料设计了以2-乙基已基膦酸单(2-乙基已基)酯(HEH(EHF),P_(507))为载体的支撑液膜迁移钴的实验,获得的数据为深入实验提供了依据.基本原理支撑液膜(SLM)是依靠微孔塑料薄膜(支撑体)微孔的毛细管作用将含萃取剂(载体)的有机溶液吸附在支撑体上.P_(507)萃取钴表示为:     

含氟共聚物与钴卟啉复合膜的制备及促进氧输送性能

研究了甲基丙烯酸八氟戊酯-乙烯基咪唑共聚物与钴卟啉复合膜的制备及钴卟啉与氧络合、促进输送性能.共聚物中的咪唑基与钴卟啉的第五配位点在溶液中络合,制得的复合膜具有快速和可逆的氧结合特性.温度降低,钴卟啉与氧络合的平衡常数增加;膜中的钴卟啉与氧络合平衡常数大于N,N-二甲基甲酰胺(DMF)溶液中的平衡常数.钴卟啉与氧络合和选择性地促进氧的输送使共聚物/钴卟啉复合膜的氧渗透系数和氧/氮选择系数提高.     

乙丙三元橡胶磺酸钴离聚体膜的富氧性能研究

通过磺化、中和反应制备了乙丙三元橡胶（ＥＰＤＭ）磺酸钴离聚体（Ｃｏ（Ⅱ） Ｓ ＥＰＤＭ）膜并研究了其富氧性能．结果发现，该膜对分子氧具有促进输送作用，其原因被认为是在离聚体中可能形成了一种高分子钴络合物结构．这种络合物在其空位上能够与分子氧进行快速可逆的结合．ＥＳＲ谱提供了钴氧结合的证据     

Polymeric complex membranes based on styrene–diene–styrene triblock copolymers for oxygen enrichment

Polymers containing a vinylpyridine, vinylimidazole or oxirane group could be used to immobilize cobalt Schiff bases (CoS), which serve as the oxygen carrier in oxygen enrichment. The graft copolymers, based on styrene–butadiene–styrene (SBS) and styrene–isoprene–styrene grafted with 4-vinylpryidine and 1-vinylimidazole, and epoxidized SBS copolymers were prepared to immobilize CoS. The equilibrium constants between CoS and polymeric materials, the oxygen coordination number and the oxygen binding constants were determined. The thermodynamic parameters of oxygen association/dissociation in various complex membranes were determined. The oxygen permeation behavior through various CoS-containing complex membranes was studied and discussed by the dual-mode facilitated transport theory. The permeation properties of oxygen and nitrogen at low pressure were also investigated.     

Nano-thin film formation on polymeric supports

Macromolecular electrolytes thin films of nanometer thickness on a surface of polymeric membrane have been prepared by a simple method using well controlled nano-sized materials such as star shaped macromolecules, brushes and dendrimers, and characterized by the gas transport properties. Metal ions in macromolecular electrolytes are readily reduced by UV irradiation to form metal nanoparticles as well as metal nanoparticle pattern adhered on a polymer support. To cite this article: J. Won et al., C. R. Chimie 6 (2003).     

Fluorophilic cobalt phthalocyanine‐containing Nafion membrane: high oxygen permeability and proton conductivity in the membrane

A multiply‐fluorinated cobalt phthalocyanine (CoFPC) was prepared, which could reversibly interact with oxygen. CoFPC was introduced into the hydrophobic perfluoroethylene‐backbone domain of the Nafion membrane. The localization of CoFPC did not reduce the high proton conductivity (10^?2–10^?3 S cm^?1) ascribed to the hydrophilic channel of Nafion. The oxygen permeability through the CoFPC/Nafion membrane was higher than the nitrogen permeability and that of the pristine Nafion membrane, and was significantly enhanced at the lower upstream pressure. The permselectivity of oxygen versus nitrogen increased beyond 20 with the CoFPC content in the membrane. The CoFPC/Nafion membrane was coated on a glassy carbon modified with a Pt/C catalyst. The high electrochemical reduction current of oxygen suggested that the CoFPC/Nafion membrane efficiently supplied oxygen to the Pt/C catalyst. Copyright © 2009 John Wiley & Sons, Ltd.     

The Influence of Electrolyte Type on Kinetics of Redox Processes in the Polymer Films of Ni(II) Salen-Type Complexes

Electrodes modified with polymers derived from the complexes [Ni(salcn)], [Ni(salcn(Me))] and [Ni(salcn(Bu))] were obtained in order to study the kinetics of electrode processes occurring in polymer films, depending on the thickness of the films, the type of electrolyte and the solvent. FTIR and EQCM methods were used to determine the type of mass transported into polymer films during anode processes and the number of moles of ions and solvent. The rate of charge transport through films was determined by the cyclic voltammetry method, by the quantity cD^1/2. It was shown that the charge transport was determined by the transport of anions. The kinetics were most efficient for poly[Ni(salcn(Bu))] modified electrodes, obtained from TBAPF₆ and working in TBAClO₄ and TBABF₄. It was also shown that a solvent with a higher DN value and lower viscosity (MeCN) facilitated the transport of the charge through polymer films.     

Sulfonated Microporous Polymer Membranes with Fast and Selective Ion Transport for Electrochemical Energy Conversion and Storage

Membranes which allow fast and selective transport of protons and cations are required for a wide range of electrochemical energy conversion and storage devices, such as proton‐exchange membrane (PEM) fuel cells (PEMFCs) and redox flow batteries (RFBs). Herein we report a new approach to designing solution‐processable ion‐selective polymer membranes with both intrinsic microporosity and ion‐conductive functionality. Polymers are synthesized with rigid and contorted backbones, which incorporate hydrophobic fluorinated and hydrophilic sulfonic acid functional groups, to produce membranes with negatively charged subnanometer‐sized confined ionic channels. The ready transport of protons and cations through these membranes, and the high selectivity towards nanometer‐sized redox‐active molecules, enable efficient and stable operation of an aqueous alkaline quinone redox flow battery and a hydrogen PEM fuel cell.     

Hybrid metal–polymer composites from functional block copolymers

The combination of metals and polymers in hybrid materials is a research area of great current interest. A number of methods for controlling the positioning of metallic species within polymer matrices on the nanometer scale have been developed. This highlight focuses on the use of functional block copolymers for the localization of metal species, especially nanoparticles, on the nanometer scale through block copolymer phase segregation. Research from the author's group on the use of alkyne‐functional block copolymers for the preparation of cobalt‐containing materials is discussed in this context. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4323–4336, 2005     

Infrared absorption enhancement of fluorinated poly‐acrylate thin films on Co‐alloy substrate

Fluorinated poly‐acrylate films coated on continuous Co‐based metal substrate show significant IR absorption enhancement. The degree of enhancement depends greatly on the type of chemical bonds in the polymer molecules and the corresponding vibrations of chemical dipoles. Strong polar groups like C? O, C? F and C?O show the strongest absorption enhancement that also coincides with significant blueshift of the corresponding IR bands. In this paper, the possible mechanism for IR absorption enhancement and band shift are discussed on the basis of the electric field intensification on metal surface, charge transfer and dipole reorientation of the polymer molecules adsorbed on the metal surface. Chemisorption of the polymer molecules on Co‐alloy is established through the interaction between the oxygen atoms in carboxylic group and the substrate cobalt atoms reacting through electron overlap and spin‐coupling of oxygen π‐orbital and cobalt d‐orbital. Copyright © 2006 John Wiley & Sons, Ltd.