Rheological studies of disulfonated poly(arylene ether sulfone) plasticized with poly(ethylene glycol) for membrane formation

Disulfonated poly(arylene ether sulfone) (BPS) random copolymers, prepared from a sulfonated monomer, have been considered for use as membrane materials for various applications in water purification and power generation. These membranes can be melt-processed to avoid the use of hazardous solvent-based processes with the aid of a plasticizer, a low molecular weight poly(ethylene glycol) (PEG). PEG was used to modify the glass transition temperature and melt rheology of BPS to enable coextrusion with polypropylene (PP). Our previous paper discussed the miscibility of BPS with PEG and the influence of PEG on the glass transition of BPS. In this study, the rheological properties of disulfonated poly(arylene ether sulfone)s plasticized with poly(ethylene glycol) (PEG) are investigated to identify coextrusion processing conditions with candidate PPs. The effects of various factors including PEG molecular weight, PEG concentration, temperature and BPS molecular weight on blend viscosity were studied. The rheological data effectively lie on the same master curve developed by Bueche and Harding for non-associating polymers such as poly(methyl methacrylate) (PMMA) and polystyrene (PS). Although sulfonated polysulfone contains ionic groups, the form of its viscosity versus shear rate (or frequency) behavior appears to be dominated by the relaxation of polymer entanglements.     

Intermolecular interaction in aqueous solution of binary blends of poly(acrylamide) and poly(ethylene glycol)

The interaction between poly(acrylamide) (PAM) and poly(ethylene glycol) (PEG) in their solid mixture was studied by Fourier transform infrared spectroscopy (FTIR); and their interaction in aqueous solution was investigated by nuclear magnetic resonance spectroscopy (NMR). For the solid PAM/PEG mixtures, an induced shift of the >C?O and >N? H in amide group was found by FTIR. These results could demonstrate the formation of intermolecular hydrogen bonding between the amide group of PAM and the ether group of PEG. In the aqueous PAM/PEG solution system, the PAM and PEG associating with each other in water, i.e., the amide group of PAM interacting with the ether group of PEG through hydrogen bonding was also found by ¹H NMR. Furthermore, the effects of different molecular weight of PAM on the strength of hydrogen bonding between PAM and PEG in water were investigated systemically. It was found that the hydrogen bonding interaction between PAM and PEG in water did not increase with the enlargement of the PAM molecular weight as expected. This finding together with the viscosity reduction of aqueous PAM/PEG solution with the PAM molecular weight increasing strongly indicated that PAM molecular chain, especially having high molecular weights preferred to form spherical clews in aqueous PEG solution. Therefore, fewer amide groups in PAM could interact with the ether groups in PEG. Based on these results, a mechanism sketch of the interaction between PAM and PEG in relatively concentrated aqueous solution was proposed. The fact that the phase separation of aqueous PAM/PEG solution occurs while raising the temperature indicates that this kind of hydrogen bonding between PAM and PEG in water is weak and could be broken by controlling the temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Application of thermo-responsive poly(methyl vinyl ether) containing copolymers in combination with ultrasonic treatment for pigment surface modification in pigment dispersions

The process of surface modification of hydrophobic organic (copper phthalocyanine (CuPc)) as well as hydrophilic inorganic pigments (titanium dioxide) in aqueous dispersions by employing tailor-made thermo-responsive copolymers and the colloidal stability have been studied as a function of temperature. The pigment surface modification is achieved by conventional adsorption and by thermoprecipitation of amphiphilic methyl vinyl ether (MVE) containing block and graft copolymers, exhibiting a lower critical solution temperature (LCST), with poly(isobutyl vinyl ether) blocks and poly(ethylene oxide) side chains, respectively. The effect of mechanical treatment of the pigment dispersion by ultrasonic power alone or in combination with the LCST property was investigated. The course of the pigment surface coating process was followed by the electrokinetic sonic amplitude (ESA) method. The temperature-controlled sorption of PMVE-g-PEO graft copolymers on both inorganic and organic pigment surfaces was investigated. It was found that ultrasonic treatment together with LCST thermoprecipitation is a promising method for the surface modification of pigments with regard to dispersion stability.     

Inhibition of bovine serum albumin adsorption by poly(ethylene glycol) soft segment in biodegradable poly(ethylene glycol)/poly(L-lactide) copolymers

The objective of this study was to investigate the effects of the incorporation of ether linkages into polylactide (PLLA) chains and the time of biodegradation on the behavior of protein adsorption. The content of poly(ethylene glycol) (PEG) in PLLA/PEG copolymers is from 4.4 to 18.3 wt %, and the length of the PEG soft segment is 1000, 2000, and 6000 daltons. The bovine serum albumin (BSA) adsorption onto the biodegradable PLLA/PEG copolymers was carried out using ultraviolet spectroscopy. The surface tension of PLLA and PLLA/PEG was measured using a contact angle. The data show that the incorporation of PEG segments makes the copolymer more polar and, therefore, leads to a reduction of protein adsorption. As the hydrolysis of polymers proceeds, both PLLA and PLLA/PEG turn out to be more polar. However, the initial compositions of degraded PLLA/PEG have a weak influence on the protein adsorption onto its hydrolyzed surface with a substantially long duration of hydrolysis. This phenomenon is attributed to the hydrophobic interaction between polar PLLA/PEG and BSA. © 1993 John Wiley & Sons, Inc.     

聚乙二醇/聚乙烯吡咯烷酮修饰的纳米Fe3O4粒子的制备与表征

为了获得能够在水中稳定分散,具有广泛应用前景的磁性纳米粒子,以不同分子量的聚乙烯吡咯烷酮(PVP)作为修饰剂,在聚乙二醇(PEG)中高温热分解乙酰丙酮铁(Fe(acac)₃)制备了纳米Fe₃O₄粒子。采用X射线粉末衍射仪(XRD)、透射电镜(TEM)、高分辨透射电镜(HRTEM)、超导量子干涉仪(SQUID)、热重分析仪(TGA)、傅里叶变换红外光谱仪(FT-IR)、纳米粒度与zeta电位分析仪对样品进行了表征,并对样品在生理盐水和生理缓冲液中的稳定性进行了研究,结果表明:制备的纳米Fe₃O₄粒子具有高的结晶度以及单分散性,在300 K下,具有超顺磁性和较高的饱和磁化强度;PEG和PVP共同修饰于纳米Fe₃O₄粒子表面,为纳米Fe₃O₄粒子提供了良好的水分散性;制备的纳米Fe₃O₄粒子在生理盐水和多种生理缓冲液中能够高度溶解并稳定地分散。水中的纳米Fe₃O₄粒子表面呈电中性,表面修饰层的空间位阻效应是所制备的纳米粒子在水溶液中高分散的原因。     

Covalent immobilization of an antimicrobial peptide on poly(ethylene) film

An antimicrobial film was produced by covalently attaching synthetic peptide E14LKK to poly(ethylene) film. E14LKK is a 14 residue, magainin‐class peptide with broad‐spectrum antimicrobial activity. The poly(ethylene) surface was first oxidized with chromic/sulphuric acid, then PEGylated by using carbodiimide chemistry to attach ω‐amino‐α‐carboxyl‐poly(ethylene glycol) (PEG). The peptide was covalently coupled to the free terminus of the PEG, again using carbodiimide coupling. Surface contact angles for distilled water decreased from 101° initially to 61° following oxidation and 45° following PEGylation. Film surface chemistry showed the expected changes during the modifications: dye adsorption assays indicated changes in the number of acidic and basic groups and X‐ray photoemission spectroscopy showed increasing oxygen and nitrogen levels. Antimicrobial activity was demonstrated in broth cultures against E.coli: growth was reduced by atleast 3 log cycles compared to controls. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Competitive mechanism of poly(ethylene glycol) with poly(vinyl methyl ether) in complexing water molecules revealed with elastic light scattering spectroscopy

By using elastic light scattering (ELS) spectroscopy, dependences of lower critical solution temperature (LCST) of poly(vinyl methyl ether) (PVME)/poly(ethylene glycol) (PEG) solutions on concentration (C _PEG) and molecular weight of PEG were analyzed. It was found that the onset temperature of phase separation (T _p) decreased with increasing C _PEG or molecular weight of PEG in the solutions. It indicated that PEG was competitive with PVME in complexing water molecules. The presence of PEG disturbed the hydration layer around PVME, facilitating the aggregation of PVME chains at lower temperature. Moreover, the ELS spectra revealed the aggregation and dissociation of molecular chains in PVME/PEG solutions during one heating and cooling cycle. PVME chains aggregated above the microphase transition temperature. With further increasing temperature, PVME aggregates started to contract, and then kept stable. During cooling, the chain aggregates were not immediately swelled but gradually swelled, and began to dissociate when the solution temperature was further decreased. Finally, the conformation of the molecular chains returned to its original state.     

Removal of nonionic surfactant by systems based on chloromethylated polystyrene–poly(ethylene glycol)

For the purpose of obtaining compounds which can remove nonionic surfactants in water, chloromethylated polystyrene (CMPS) was allowed to react with triethylene glycol monomethyl ether (3EGMME), tetraethylene glycol (4EG), poly(ethylene glycol) (PEG) 200, 400, 600, 1000, and 1500. The amount of PEG groups combined with CMPS decreased with an increase in the molecular weight of PEG. The ability of the product to remove polyethylene glycol mono-p-nonyl phenyl ether (NP, n = 10), a nonionic surfactant, solutes in water was greater in the product with PEG of greater MW than that with PEG of smaller MW, and in the product with more PEG groups (mol/g prod.) than in that with less PEG groups. The removal behavior of the products conformed to Freundlich's adsorption formula. Constants of the formula, the effect of temperature on the constants, the effect of combined PEG groups on the removed amount, and the removal manner were studied.     

Improvement of biocompatibility and biodegradability of poly(ethylene succinate) by incorporation of poly(ethylene glycol) segments

Poly(ethylene glycol) (PEG) segments were incorporated into poly(ethylene succinate) (PES) by chain-extension reaction of PEG with PES using 1,6-hexamethylene diisocyanate as a chain-extender, forming a poly(ester ether urethane) (PEEU). The chemical structures and molecular weights of the PEEUs were determined by ¹H NMR and GPC, respectively. The composition dependence of thermal transitions, crystallization, hydrophilicity, in vitro biocompatibility, in vitro biodegradation and tensile properties of the PEEUs were systematically investigated. The glass transition temperature and degree of crystallinity of PEEU decreased with increase of PEG content. The hydrophilicity increased with PEG content as proved by the decreased water contact angle and increased water absorption. The results of cell culturing suggested that the in vitro biocompatibility increased with PEG content. Hydrolytic degradation demonstrated that degradation rate of PEEU increased with PEG content, which was caused by the increased hydrophilicity and decreased degree of crystallinity with increase of PEG content. The tensile results proved that the tensile strength and modulus decreased while elongation at break increased with PEG content.     

Physicochemical characterization of poly(ethylene glycol) plasticized poly(methyl vinyl ether‐co‐maleic acid) films

The influence of the poly(ethylene glycol) (PEG) plasticizer content and molecular weight on the physicochemical properties of films cast from aqueous blends of poly(methyl vinyl ether‐co‐maleic acid) (PMVE/MA) was investigated with tensile mechanical testing, thermal analysis, and attenuated total reflectance/Fourier transform infrared spectroscopy. Unplasticized films and those containing high copolymer contents were very difficult to handle and proved difficult to test. PEG with a molecular weight of 200 Da was the most efficient plasticizer. However, films cast from aqueous blends containing 10% (w/w) PMVE/MA and either PEG 1000 or PEG 10,000 when the copolymer/plasticizer ratio was 4 : 3 and those cast from aqueous blends containing 15% (w/w) PMVE/MA and either PEG 1000 or PEG 10,000 when the copolymer/plasticizer ratio was 2 : 1 possessed mechanical properties most closely mimicking those of a formulation we have used clinically in photodynamic therapy. Importantly, we found previously that films cast from aqueous blends containing 10% (w/w) PMVE/MA performed rather poorly in the clinical setting, where uptake of moisture from patients' skin led to reversion of the formulation to a thick gel. Consequently, we are now investigating films cast from aqueous blends containing 15% (w/w) PMVE/MA and either PEG 1000 or PEG 10,000, where the copolymer/plasticizer ratio is 2 : 1, as possible Food and Drug Administration approved replacements for our current formulation, which must currently be used only on a named patient basis as its plasticizer, tripropylene glycol methyl ether, is not currently available in pharmaceutical grade. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electrospun fibers from functional polyglycidol/poly(ε-caprolactone) blends with defined surface properties

Highly hydrophilic but water insoluble fibers from star-shaped poly(ethoxyethyl glycidyl ether) and poly(ε-caprolactone) polymer blends in the submicron range were prepared using the electrospinning technique. The fibers were achieved in a smooth and homogeneous manner and do show tremendous decreased protein adsorption. Additionally, using alkyne- or vinyl sulfonate end capped polymer, fibers with the correspondent surface reactivity have been prepared. All fibers showed high biocompatibility and were highly hydrophilic but water stable. Furthermore, nonwovens based on functionalized poly(ethoxyethyl glycidyl ether) were equipped with small biofunctional molecules, e.g., the peptide sequence glycine-arginine-glycine-aspartate-serine (GRGDS). These fibers showed increased cell attachment compared with nonfunctionalized nonwovens. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Polymeric systems for acoustic damping. III. Blends of poly(vinyl chloride), segmented poly(ether ester), and poly(methyl acrylate)

A solution blend of poly(vinyl chloride) and a segmented poly(ether ester) and blends containing these two polymers plus poly(methyl acrylate) were investigated by dynamic mechanical analysis and electron microscopy. The binary blend, which contained 75% by weight of the poly(ether ester), showed only one loss peak, but also evidence of some phase separation. It is believed that the polyether sequences of the poly(ether ester) are extensively mixed with poly(vinyl chloride). Poly(methyl acrylate) was added to spread the damping range and produce a material of potential use as an acoustic damper. It is evident from both electron microscopy and dynamic mechanical analysis that poly(methyl acrylate) is substantially incompatible in the other polymers.     

Hydrophilic interpolymer membranes from crosslinked blends of poly(vinylalcohol), poly(styrene sodium sulfonate) and poly(vinyl methyl ether–alt–maleic anhydride)

Interpolymer ion exchange membranes were prepared from a compatible casting solution that contained poly(styrene sodium sulfonate), poly(vinyl methyl ether–alt–maleic anhydride), and poly(vinyl alcohol). Crosslinking of the films was accomplished through the formation of ester linkages that were stable in aqueous environments. Membrane properties (water content, capacity, concentration potential, equivalent conductivity) were measured over a wide range of membrane compositions. Ultrafiltration was carried out with a feed solution that was 0.01N in KCI and 15 ppm in erythrosin. Rejection and hydraulic permeability data were reported as a function of membrane composition.     

Nanocomposite polymer electrolytes containing silica nanoparticles: Comparison between poly(ethylene glycol) and poly(ethylene oxide) dimethyl ether

Nanocomposite polymer electrolytes consisting of low molecular weight poly(ethylene oxide) (PEO), iodine salt MI (M = K⁺, imidazolium⁺), and fumed silica nanoparticles have been prepared and characterized. The effect of terminal group in PEO, i.e., hydroxyl (? OH) and methyl (CH₃) using poly(ethylene glycol) (PEG) and PEO dimethyl ether (PEODME), respectively, was investigated on the interactions, structures, and ionic conductivities of polymer electrolytes. Wide angle X‐ray scattering (WAXS), differential scanning calorimetry (DSC), and complex viscositymeasurements clearly showed that the gelation of PEG electrolytes occurred more effectively than that of PEODME electrolytes. It was attributed to the fact that the hydroxyl groups of PEG participated in the hydrogen‐bonding interaction between silica nanoparticles, and consequently helped to accelerate the gelation reaction, as confirmed by FTIR spectroscopy. Because of its interaction, the ionic conductivities of PEG electrolytes (maximum value ～ 6.9 × 10^?4 S/cm) were lower than that of PEODME electrolytes (2.3 × 10^?3 S/cm). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis of hydrophilic poly(vinyl ether)s and their application for separation media design

Poly(2-acetoxyethyl vinyl ether (AcOVE)) and poly(2-acetoxyethyl vinyl ether-co-2-vinyloxyethyl phthalimide) were synthesized by traditional cationic polymerization, typically at −20°C in toluene with BF₃O(C₂H₅)₂ as initiator, to give polymers with degrees of polymerization (Dp) in the range of 600–1100. In addition, poly(AcOVE) was polymerized by controlled cationic polymerization at 0°C with molecular weights in a predetermined fashion. The Dp's were calculated from Dp = [M]₀/[I]₀ and typical values were 5, 10, 100 and 200. The molecular weight values obtained for a theoretical Dp = 200, were for poly(2-acetoxyethyl vinyl ether), M_n = 19,200, M_w = 22,700 and POLYDISPERSITY = 1.2, as determined by GPC. The deprotected hydrophilic polymers, poly(2-hydroxyethyl vinyl ether) and poly(2-hydroxyethyl vinyl ether-co-2-aminoethyl vinyl ether), were used for the preparation of novel gel filtration media as well as new anion exchangers. In the case of gel filtration, poly(2-hydroxyethyl vinyl ether) was attached to a beaded agarose matrix (34 μm), i.e. Sepharose® HP. It was shown that the attachment of the poly(vinyl ether) affected the selectivity. In gel filtration of selected biomolecules, the poly(vinyl ether) modified agarose matrix showed performance characteristics comparable to the reference used, i.e. Superdex® 30 prep grade. In addition the poly(vinyl ether)s were shown to be stable in a wide pH-range. The stability was confirmed by the conclusion that no changes in molecular weight were observed after treatment with 0.1 M HCl (pH = 1) or 0.01 M NaOH (pH = 12) for six weeks at 40°C. For the preparation of anion-exchanger media, the beads containing poly(2-hydroxyethyl vinyl ether) was further modified with a quaternary ammonium group, to produce a separation media having a high dynamic binding capacity for bovine serum albumin (BSA).     

PEG-modified magnetic hypercrosslinked poly(styrene-co-divinylbenzene) microspheres to minimize sorption of serum proteins

Monodisperse poly(styrene-co-divinylbenzene) [P(St-DVB)] microspheres were prepared by the precipitation polymerization of styrene (St) and divinylbenzene (DVB) in acetonitrile (ACN). Effect of St/DVB ratio and monomer concentration on morphology and particle size was investigated. Monodisperse 4.1 μm P(St-DVB) microspheres were chloromethylated with chloromethyl methyl ether (CMME) and hypercrosslinked using anhydrous FeCl₃ as a catalyst to form a very fine porous structure and to introduce reactive chloromethyl groups in the resulting product denoted as HC-P(St-DVB) particles. The hypercrosslinked microspheres were then functionalized with amino groups to yield HC-P(St-DVB)-NH₂ particles and iron oxide was precipitated within their pores. The obtained microparticles were highly magnetic with iron content ～38 wt% Fe. The surface of the magnetic microspheres was newly hydrophilized with methoxy-poly(ethylene glycol) (methoxy-PEG) which was confirmed by ATR FT-IR spectroscopy. The poly(ethylene glycol) (PEG)-modified magnetic microspheres were investigated in terms of sorption of serum proteins under different conditions and compared with the sorption on neat magnetic HC-P(St-DVB)-NH₂ particles. The surface modification of magnetic microspheres significantly minimized the adsorption of the serum proteins.     

Synthesis and characterization of complexes between poly(itaconic acid) and poly(ethylene glycol)

Summary Interpolymer complexes of poly(itaconic acid) and poly(ethylene glycol) (PIA/PEG) were prepared by two different procedures: simple mixing of preformed PIA and PEG and by polymerization of itaconic acid on poly(ethylene glycol) as a template. Complex formation was attributed to hydrogen bond formation between the carboxyl group of PIA and the ether group of PEG. The two types of complexes were characterized by viscometric measurements, thermogravimetric analysis (TGA), Fourier-transform infrared (FTIR) spectroscopy and adhesive force measurements. The results indicate that complexes prepared by template polymerization have a stronger hydrogen bonding and hence more ordered structure and better mucoadhesive properties.     

Properties of Poly(vinyl chloride)/poly(ethylene oxide)/polyaniline Conductive Films: The Effect of Poly(ethylene glycol) Diglycidyl Ether

The effect of polyaniline and poly(ethylene glycol) diglycidyl ether on tensile properties, morphology, thermal degradation, and electrical conductivity of poly(vinyl chloride)/poly(ethylene oxide)/polyaniline conductive films was studied. The poly(vinyl chloride)/poly(ethylene oxide)/polyaniline conductive films were prepared using a solution casting technique at room temperature until a homogeneous solution was produced. Poly(vinyl chloride)/poly(ethylene oxide)/polyaniline/poly(ethylene glycol) diglycidyl ether conductive films exhibit higher electrical properties, tensile strength, modulus of elasticity but lower final decomposition temperature than poly(vinyl chloride)/poly(ethylene oxide)/polyaniline conductive films. Scanning electron microscopy morphology showed that the polyaniline more widely dispersed in the poly(vinyl chloride)/poly(ethylene oxide) blends with the addition of poly(ethylene glycol) diglycidyl ether as surface modifier.     

Structural characterization and luminescent properties of poly(p-phenylene vinylene) and poly(ethylene glycol) blends

The luminescent properties of poly(p-phenylenevinylene) (PPV) blending with poly (ethylene glycol) (PEG) were investigated in terms of their structural formation during sample preparation. The blended systems were prepared from an aqueous solution of water-soluble poly (xylylene tetrahydrothiophenium chloride) (PPV precursor) mixed with PEG, followed by heat treatment to remove the tetrahydrothiophene groups from the PPV precursor. Structural analysis showed that PEG could react with PPV precursor to form C-O-C linkage and carbonyl groups in PPV chains, interrupting their conjugated length as suggested by their Infrared, Raman and UV/vis spectroscopes. Wide angle X-ray scattering (WARS) of blended systems also showed that PPV in blends had less packing. As to luminescent properties, the UV/vis and photoluminescent (PL) spectra show that the energy gap needed to produce the excitons increased along with the increase of PL intensity when PPV was blended with PEG. Similar results were also found for the EL properties of ITO/polyblends/Al devices. The EL light emission from blends was blue-shifted (compared to PPV) with a rather low threshold electric field strength. The EL performance of polyblends was better than that of pure PPV. Among them, the PPV-50PEG showed the highest EL intensity. The improved EL efficiency was attributed to the dilution effect, interrupted conjugated length, and lower packing of PPV chains.     

Structure and dielectric properties of poly(vinyl chloride) thermoplastic elastomer blends

The structure, development, morphology, and dielectric relaxation have been investigated in poly(vinyl chloride)–thermoplastic elastomer (copolyester–ether) blends having different compositions. The changes in the intensities of dielectric relaxation peaks for the β and γ processes with respect to blend composition have been found to be associated with corresponding changes in crystalline structure and morphology of the elastomeric component. The critical composition for observing such modification of properties is about 50% of poly(vinyl chloride) above which the blend becomes almost amorphous. © 1994 John Wiley & Sons, Inc.