THERMODYNAMICS OF POLY(ETHYLENE OXIDE)-POLY(VINYL ACETATE) BLENDS

Heat-of-mixing data, obtained on blends of poly(ethylene oxide) (PEO) with whole and fractionated poly(vinyl acetate) (PVAc), were used to feed Patterson's theory of polymer-polymer miscibility. Negative values of mixing enthalpy, contact-energy term, interaction'' parameter and excess volume were obtained only for blends with the lowest molecular weight PVAc fraction. These results show that miscibility of PVAc with PEO strongly depends on its molecular weight. The calculated unfavourable excess volume term of the Patterson equation is small in comparison with the absolute value of the interaction term. Therefore, miscibility of PEO and low-molecular-weight PVAc is dictated by the weak specific interactions between different repeat units and by the entropic gain in the mixing process.

MISCIBILITY AND PHASE-BEHAVIOR IN BLENDS OF POLY(HYDROXYETHER OF BISPHENOL-A) WITH POLY(ETHYLENE OXIDE-CO-PROPYLENE OXIDE)

The miscibility of poly(hydroxyether of bisphenol A) (phenoxy) with a series of poly(ethylene oxide-co-propylene oxide) (EPO) has been studied. It was found that the critical copolymer composition for achieving miscibility with phenoxy around 60-degrees-C is about 22 mol % ethylene oxide (EO). Some blends undergo phase separation at elevated temperatures, but there is no maximum in the miscibility window. The mean-field approach has been used to describe this homopolymer/copolymer system. From the miscibility maps and the melting-point depression of the crystallizable component in the blends, the binary interaction energy densities, B(ij), have been calculated for all three pairs. The miscibility of phenoxy with EPO is considered to be caused mainly by the intermolecular hydrogen-bonding interactions between the hydroxyl groups of phenoxy and the ether oxygens of the EO units in the copolymers, while the intramolecular repulsion between EO and propylene oxide units in the copolymers contributes relatively little to the miscibility.

RADIATION-INDUCED CROSS-LINKING OF POLY(METHYL METHACRYLATE)-POLY(ETHYLENE OXIDE) BLEND

Radiation-induced crosslinking of poly(methyl methacrylate) (PMMA)-poly(methylene oxide) (PEO) blends was studied. It was found that PMMA in PMMA-PEO blend can be crosslinked in the range of certain doses (1 approximately 20 x 10(4) Gy) and composition (PMMA% = 30 approximately 70) under the absence of oxygen. Moreover, it was also found that the crosslinking degree of PMMA in the blend in which the content of PMMA is 70% is the largest. The crosslinking degree of PMMA in the blend is closely related with the polymer miscibility. The crosslinking degree of the blend prepared at 60-degrees-C is far higher than one at ambient temperature.

THE MISCIBILITY AND MORPHOLOGY OF EPOXY-RESIN POLY(ETHYLENE OXIDE) BLENDS

Poly(ethylene oxide) (PEO) was found to be miscible with uncured epoxy resin, diglycidyl ether of bisphenol A (DGEBA), as shown by the existence of a single glass transition temperature (T(g)) in each blend. However, PEO with M(n) = 20 000 was judged to be immiscible with the highly amine-crosslinked epoxy resin (ER). The miscibility and morphology of the ER/PEO blends was remarkably affected by crosslinking. It was observed that phase separation in the ER/PEO blends occurred as the crosslinking progressed. This is considered to be due to the dramatic change in the chemical and physical nature of ER during the crosslinking.

COMPATIBILIZING EFFECT OF POLY(ETHYLENE OXIDE)-B-POLYSTYRENE-B-POLY(ETHYLENE OXIDE) IN PHENOLPHTHALEIN POLY(ETHER ETHER KETONE) POLY(2,6-DIMETHYL-1,4-PHENYLENE OXIDE) BLENDS

The morphology and mechanical behaviour of phenolphthalein poly(ether ether ketone) (PEK-C)/poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) blends has been investigated. A poly(ethylene oxide)-b-polystyrene-b-poly(ethylene oxide) (PEO-PS-PEO) triblock copolymer was used as compatibilizer. It was found that PEO-PS-PEO has a compatibilizing effect on the PEK-C/PPO blends. The addition of PEO-PS-PEO to the blends greatly improves phase dispersion and interfacial interfacial adhesion and also enhances the ultimate tensile strength and Young's modulus at compositions ranging from 30 to 70% PEK-C. However, all the values of the ultimate tensile strength within the whole composition range are lower than those expected by simple additivity, probably owing to the poor mechanical properties of PEO-PS-PEO copolymer.

Characterization of polyethylene glycol-modified proteins by semi-aqueous capillary electrophoresis

A new program to characterize polyethylene glycol-modified (PEGylated) proteins is outlined using capillary zone electrophoresis (CZE). PEGylated ribonuclease A and lysozyme were selected as examples. Five separation procedures were compared to select out the mixed buffer of acetonitrile-water (1:1, v/v) at pH 2.5 as the best to characterize the PEGylated proteins without sample pretreatment. Polyethylene oxide (PEO) with a high molecular mass of 8X10(6) was applied to rinse the capillary to form a dynamic coating which would decrease the undesirable proteins adsorbed to the inner wall of the silica. The electroosmotic flow (EOF) mobility of the five procedures was determined, respectively. It is found that acetonitrile is mainly responsible for the good resolution of PEGylated proteins with the help of PEO coating in the semi-aqueous system. The low EOF mobility and current in the semi-aqueous system might also have some responsibility for the high resolution. The semi-aqueous procedure described in this paper also demonstrates higher resolution of natural proteins than aqueous ones. (C) 2001 Elsevier Science B.V. All rights reserved.

Surface Initiated Polymerization from Substrates of Low Initiator Density and Its Applications in Biosensors

Surface initiated polymerization (SIP) has become an attractive method for tailoring physical and chemical properties of surfaces for a broad range of applications. Most of those application relied on the merit of a high density coating. In this study we explored a long overlooked field of SIP. SIP from substrates of low initiator density. We combined ellipsometry with AFM to investigate the effect of initiatior density and polymerization time on the morphology of polymer coatings. In addition, we carefully adjusted the nanoscale separation of polymer chains to achieve a balance between nonfouling and immobilization capacities. We further tested the performance of those coating on various biosensors, such as quartz crystal microbalance, surface plasmon resonance, and protein microarrays. The optimized matrices enhanced the performance of those biosensors. This report shall encourage researches to explore new frontiers in SIP that go beyond polymer brushes.

PEGylated Phospholipid Membrane on Polymer Cushion and Its Interaction with Cholesterol

By employing poly(ethylene glycol) (PEG) shielding and a polymer cushion to achieve air stability of the lipid membrane, we have analyzed PEG influence on dried membranes and the interaction with cholesterol. Small unilamellar vesicles (SUVs) formed by the mixture of 1,2-dimyristoylphosphatidylcholine (DMPC) with different molar fraction of 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(poly(ethylene glycol))-2000] (DSPE-PEG(2000)) adsorb and fuse into membranes on different polymer-modified silicon dioxide surfaces, including chitosan, poly(L-lysine) (PLL), and hyaluronic acid, Dried membranes arc further examined by ellipsometer and atomic force microscopy (AFM). Only chitosan can support a visible and uniform lipid array. The thickness of dry PEGylated lipid membrane is reduced gradually as the molar fraction of PEG increases. AFM scanning confirms the lipid membrane stacking for vesicles containing low PEG, and only a proper amount of PEG can maintain a single lipid hi lover; however, the air stability of the membrane will be destroyed if overloading. PEG. Cholesterol incorporation can greatly improve the structural stability of lipid membrane, especially for those containing high molar fraction of PEG. Different amounts of cholesterol influence the thickness and surface morphology of dried membrane.

Microencapsulation of n-eicosane as energy storage material

For heat energy storage application, polyurea. microcapsules containing phase change material, n-eicosane, were synthesized by using interfacial polymerization method with toluene- 2,4-diisocyanate (TDI) and diethylenetriamine (DETA) as monomers in an emulsion system. Poly(ethylene glycol)octyl-phenyl ether (OP), a nonionic surfactant, was the emulsifier for the system. The experimental result indicates that TDI was reacted with DETA in a mass ratio of 3 to 1. FT-IR spectra confirm the formation of wall material, polyurea, from the two monomers, TDI and DETA. Encapsulation efficiency of n-eicosane is about 75%. Microcapsule of n-eicosane melts at a temperature close to that of n-eicosane, while its stored heat energy varies with core material n-eicosane when wall material fixed. Thermo-gravimetric analysis shows that core material n-eicosane, micro-n-eicosane and wall material polyurea can withstand temperatures up to 130, 170 and 250 degreesC, respectively.

Dynamic mechanical properties of gel polymer electrolytes containing ionic liquid

The copolymer of acrylonitrile (AN), methyl methacrylate (MMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMEMA) is synthesized in 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF(4)). The dynamic mechanical properties of the resulting gel polymer electrolytes containing ionic liquid are measured.

Square lamellar structure having phase-separated microdomain in H-shaped block copolymer thin film

The morphology of a H-shaped block copolymer (poly(ethylene glycol) backbone and polystyrene branches (PS)(2)PEG(PS)(2)) in a thin film has been investigated. A peculiar square lamella that has a phase-separated microdomain at its surface is obtained after spin coating. The experimental temperature plays a critical role in the lamellar formation. The copolymer first self-assembles into square lamellar micelles with an incomplete crystalline core due to the crystallizability of PEG.