THERMODYNMICS AND STRUCTURE OF POLY(ETHYLENE OXIDE) IN MIXTURES OF WATER AND ETHANOL

Poly(ethylene oxide) (PEO) is one of the most researched synthetic polymers due to the complex behavior which arises from the interplay of the hydrophilic and hydrophobic sites on the polymer chain. PEO in ethanol forms an opaque gel-like mixture with a partially crystalline structure. Addition of a small amount of water disrupts the gel: 5 wt % PEO in ethanol becomes a transparent solution with the addition of 4 vol % water. The phase behavior of PEO in mixed solvents have been studied using small-angle neutron scattering (SANS). PEO solutions (5 wt % PEO) which contain 4 vol % - 10 vol % (and higher) water behave as an athermal polymer solution and the phase behavior changes from UCST to LCST rapidly as the fraction of water is increased. 2 wt % PEO in water and 10 wt % PEO in ethanol/ water mixtures are examined to assess the role of hydration. The observed phase behavior is consistent with a hydration layer forming upon the addition of water as the system shifts from UCST to LCST behavior. At the molecular level, two or three water molecules can hydrate one PEO monomer (water molecules form a sheath around the PEO macromolecule) which is consistent with the suppression of crystallization and change in the mentioned phase behavior as observed by SANS. The clustering effect of aqueous PEO solution (M.W of PEO = 90,000 g/mol) is monitored as an excess scattering intensity at low-Q. Clustering intensity at Q = 0.004 Å^-1 is used for evaluating the clustering effect. The clustering intensity is proportional to the inverse temperature and levels off when the temperature is less than 50 ˚C. When the temperature is increased over 50 ˚C, the clustering intensity starts decreasing. The clustering of PEO is monitored in ethanol/ water mixtures. The clustering intensity increases as the fraction of water is increased. Based on the solvation intensity behavior, we confirmed that the ethanol/ water mixtures obey a random solvent mixing rule, whereby solvent mixtures are better at solvating the polymer that any of the two solvents. The solution behavior of PEO in ethanol was investigated in the presence of salt (CaCl2) using SANS. Binding of Ca2+ ions to the PEO oxygens transforms the neutral polymer to a weakly charged polyelectrolyte. We observed that the PEO/ethanol solution is better solvated at higher salt concentration due to the electrostatic repulsion of weakly charged monomers. The association of the Ca2+ ions with the PEO oxygen atoms transforms the neutral polymer to a weakly charged polyelectrolyte and gives rise to repulsive interactions between the PEO/Ca2+ complexes. Addition of salt disrupts the gel, which is consistent with better solvation as the salt concentration is increased. Moreover, SANS shows that the phase behavior of PEO/ethanol changes from UCST to LCST as the salt concentration is increased.

Solid-state nanocrystalline dye-sensitized solar cell using 2-mercapto benzimidazole doped poly(ethylene oxide) as a new polymer electrolyte

New composite doped poly (ethylene oxide) polymer electrolyte was developed using 2-mercapto benzimidazole as plasticizer and iodide/triiodide as redox couple. The fabrication of the cell involves Poly(ethylene oxide)/ 2-mercapto benzimidazole / iodide/triiodide as polymer electrolyte in dye-sensitized solar cell fabricated with N3 dye and TiO2 nanoparticles as the photoanode and Platinum coated FTO (fluorine doped SnO2) as counter electrode. The current-volatage characteristics under simulated sunlight AM1.5 shows a short circuit current Isc of 8.7mA and open circuit photovoltage 508 mV. The conductivity measurements for the new polymer electrolyte and the photoelectrochemical measurments were carried out systematically. In 2-mercapto benzimidazole the electron rich sulphur and nitrogen atoms, act as pi-electron donors that form good interaction with iodine which plays a vital role in the performance of the fabricated dye-sensitized solar cells. The resonance effect increases the stability of the cell to a considerable extent. These results suggest that the new composite polymer electrolyte performs as a promising new doped polymer-electrolyte.

Increased charge transfer of Poly (ethylene oxide) based electrolyte by addition of small molecule and its application in dye-sensitized solar cells

A Poly (ethylene oxide) based polymer electrolyte impregnated with 2-Mercapto benzimidazole was comprehensively characterized by XRD, UV–visible spectroscopy, FTIR as well as electrochemical impedance spectroscopy. It was found that the crystallization of PEO was dramatically reduced and the ionic conductivity of the electrolyte was increased 4.5 fold by addition of 2-Mercapto benzimidazole. UV–visible and FTIR spectroscopes indicated the formation of charge transfer complex between 2-Mercapto benzimidazole and iodine of the electrolyte. Dye-sensitized solar cells with the polymer electrolytes were assembled. It was found that both the photocurrent density and photovoltage were enhanced with respect to the DSC without 2-Mercapto benzimidazole, leading to a 60% increase of the performance of the cell.

Studies on aluminum-isopropoxide doped poly(ethylene oxide), poly(vinyl alcohol), and poly(ethylene oxide)-poly(vinyl alcohol) blends

Poly( ethylene oxide), poly(vinyl alcohol): and their blend in a 40 : 60 mole ratio were doped with aluminum isopropoxide. Their structural, thermal, and electrical properties were studied. Aluminum isopropoxide acts as a Lewis acid and thus significantly influences the electrical properties of the polymers and the blend. It also acts as a scavanger for the trace quantities of water p-resent in them, thereby reducing the magnitude of proton transport. It also affects the structure of polymers that manifests in the thermal transformation and decomposition characteristics.

Synthesis and micellization of star-like hyperbranched polymer with poly(ethylene oxide) and Poly(epsilon-caprolactone) arms

Novel star-like hyperbranched polymers with amphiphilic arms were synthesized via three steps. Hyperbranched poly(amido amine)s containing secondary amine and hydroxyl groups were successfully synthesized via Michael addition polymerization of triacrylamide (TT) and 3-amino-1,2-propanediol (APD) with feed molar ratio of 1:2. H-1, C-13, and HSQC NMR techniques were used to clarify polymerization mechanism and the structures of the resultant hyperbranched polymers

Crystallization and morphology of poly(ethylene oxide-b-lactide) crystalline-crystalline diblock copolymers

The crystallization behaviors and morphology of asymmetric crystalline-crystalline diblock copolymers poly(ethylene oxide-lactide) (PEO-b-PLLA) were investigated using differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), and microscopic techniques (polarized optical microscopy (POM) and atomic force microscopy (AFM)). Both blocks of PEO5-b-PLLA(16) can be crystallized, which was confirmed by WAXD, while PEO block in PEO5-b-PLLA(30) is difficult to crystallize because of the confinement induced by the high glass transition temperature and crystallization of PLLA block with the microphase separation of the block copolymer.

Synthesis and Characterization of Coil-Rod-Coil Triblock Copolymers Comprising Fluorene-Based Mesogenic Monodisperse Conjugated Rod and Poly(ethylene oxide) Coil

A series of coil-rod-coil triblock copolymers (i.e., F3T8EO8, F3T8EO17, F3T8EO45, and F3T8EO125) with a mesogenic monodisperse conjugated oligomer comprising 3 fluorene, 8 thiophene, and 2 phenyl units as the rod and poly(ethylene oxide) (PEO) as the coil were synthesized. A reference compound, that is F3T8ME2, with the identical rod but without PEO was also prepared for comparison. The volume fraction of PEO (f(PEO)) was 0, 0.16, 0.28, 0.50, and 0.73 for F3T8ME2, F3T8EO8, F3T8EO17, F3T8EO45, and F3T8EO125, respectively. It was found that the introduction of PEO into the triblock copolymers encouraged the formation of H-type aggregation and f(PEO)-dependent highly ordered mesophases while f(PEO) < 0.73. For F3T8ME2, only nematic mesophase was observed. In contrast, F3T8EO8 and F3T8EO17, with f(PEO) of 0.16 and 0.28, respectively, are smectic A (SA) mesomorphism.

Crystal Growth Transition from Flat-On to Edge-On Induced by Solvent Evaporation in Ultrathin Films of Polystyrene-b-Poly(ethylene oxide)

The transition of lamellar crystal orientation from flat-on to edge-on in ultrathin films of polystyrene-b-poly(ethylene oxide) (PS-b-PEO) via solvent vapor (toluene) treatment Was investigated. When the as-prepared film was treated in saturated solvent vapor, breakout crystals could form quickly, and then they transformed from square single crystals (flat-on lamellae) to dendrites and finally to nanowire crystals (edge-on lamellae). Initially, heterogeneous nucleation tit the polymer/substrate interface dominated the structure evolution, leading to flat-on lamellar crystals orientation. And the transition from faceted habits to dendrites indicated a transition of underlying mechanism from nucleation-controlled to diffusion-limited growth. As the solvent molecules gradually diffused into the polymer/substrate interface, it will subsequently weaken the polymer-substrate interaction.

Synthesis and self-assembly of poly(ethylene oxide)-b-poly(2-hydroxyethyl methacrylate)

Poly(ethylene oxide)-b-poly(2-hydroxyethyl methacrylate) (PEO-b-PHEMA) was synthesized by successive atom transfer radical polymerization (ATRP) of 2-hydroxyethyl methacrylate(HEMA) monomer using PEO-Br macroinitiator as initiator, CuBr/CuBr2 and 2,2.-bipyridyl (bpy) as catalyst and ligand. IR, H-1 NMR, and GPC analysis indicate that PEO-b-PHEMA block copolymer with low polydispersity index (M-w/M-n approximate to 1.1) has been formed. Self-assembly of this double hydrophilic block copolymer in the selective solvent and water was also studied. Owing to the high hydrophilic nature of the PEO and PHEMA blocks, this double hydrophilic block copolymer cannot disperse well in water. So block copolymer was modified by part esterification of PEO-b-PHEMA with acetic anhydride, which increased the hydrophobic group of the PHEMA block. The TEM results show that this block copolymer spontaneously form well-defined micelles in water.

The study of synthesis of poly(ethylene oxide)-b-poly(N,N-dimethylacrylamide) by atom transfer radical polymerization and self-assembly in selective solvents

Poly( ethylene oxide)-b-poly(N, N-dimethylacrylamide) (PEO-b-PDMA) was synthesized by successive atom transfer radical polymerization (ATRP) of N, N-dimethylacrylamide (DMA) monomer using PEO-Br macro initiators as initiator, CuBr and 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazamacrocyclotetra decane (Me-6[14] aneN(4)) as catalyst and ligand. PEO-Br macroinitiator was synthesized by esterification of PEO with 2-bromoisobutyryl bromide. GPC and H-1 NMR studies show that the plot of ln([DMA](0)/[ DMA]) against the reaction time is linear, and the molecular weight of the resulting PDMA increased linearly with the conversion. Within 3 h, the polymerization can reach almost 60% of conversion. PEO-b-PDMA copolymer with low polydispersity index (M-w/M-n approximate to 1.1) is obtained. Self-assembly of PEO-b-PDMA in selective solvents is also studied. It could self-assemble into micelles in methanol/acetone (1/10, v/v) solution. TEM analyses of the PEO-b-PDMA micelles with narrow size distribution revealed that their size and shape depend much on the copolymer composition.

Crystallization and ring-banded spherulite morphology of poly(ethylene oxide)-block-poly(epsilon-caprolactone) diblock copolymer

The crystallization behavior of crystalline-crystalline diblock copolymer containing poly(ethylene oxide) (PEO) and poly(epsilon-caprolactone) (PCL), in which the weight fraction of PCL is 0.815, has been studied via differential scanning calorimeter (DSC), wide-angle X-ray diffraction (WAXD), and polarized optical microscopy (POM). DSC and WAXD indicated that both PEO and PCL blocks crystallize in the block copolymer. POM revealed a ring-banded spherulite morphology or the PEO-b-PCL diblock copolymer.

Crystallization kinetics in shearing-induced oriented and stretched poly(ethylene oxide)

Isothermal crystallization kinetics in the melting of poly(ethylene oxide) (PEO) were investigated as a function of the shear rate and crystallization temperature by optical microscopy. The radial growth rates of the spherulites are described by a kinetics equation including shearing and relaxation combined effects and the free energy for the formation of a secondary crystal nucleus. The free-energy difference between the liquid and crystalline phases increased slightly with rising shearing rates. The experimental findings showed that the influence of the relaxation of PEO, which is related to the shear-induced orientation and stretch in a PEO melt, on the rate of crystallization predominated over the influence of the shearing. This indicated that the relaxation of PEO should be more important so that the growth rates increase with shearing, but it was nearly independent of the shear rate within the measured experimental range.

Synthesis of a novel structural triblock copolymer of poly(gamma-benzyl-L-glutamic acid)-b-poly(ethylene oxide)-b-poly(epsilon-caprolactone)

A novel structural triblock copolymer of poly(gamma-benzyl-L-glutamic acid)-b-poly(ethylene oxide)-b-poly(epsilon-caprolactone) (PBLG-PEO-PCL) was synthesized by a new approach in the following three steps: (1) sequential anionic ring opening polymerization (ROP) of ethylene oxide and epsilon-caprolactone with an acetonitrile/potassium naphthalene initiator system to obtain a diblock copolymer CN-PEO-PCL with a cyano end-group; (2) conversion of the CN end-group into NH2 end-group by hydrogenation to obtain NH2-PEO-PCL; (3) ROP of gamma-benzyl-L-glutamate-N-carboxyanhydrides (Bz-L-GluNCA) with NH2-PEO-PCL as macroinitiator to obtain the target triblock copolymer. The structures from CN-PEO precursor to the triblock copolymers were confirmed by FT-IR and H-1 NMR spectroscopy, and their molecular weights were measured by gel permeation chromatography. The monomer of Bz-L-GluNCA can react almost quantitatively with the amino end-groups of NH2-PEO-PCL macroinitiator by ROP.