Miscibility of polystyrene with poly(ethylene oxide) and poly(ethylene glycol)

The intrinsic viscosity of polystyrene–poly(ethylene oxide) (PS–PEO) and PS–poly(ethylene glycol) (PEG) blends have been measured in benzene as a function of blend composition for various molecular weights of PEO and PEG at 303.15 K. The compatibility of polymer pairs in solution were determined on the basis of the interaction parameter term, Δb, and the difference between the experimental and theoretical weight-average intrinsic viscosities of the two polymers, Δ[η]. The theoretical weight-average intrinsic viscosities were calculated by interpolation of the individual intrinsic viscosities of the blend components. The compatibility data based on [η] determined by a single specific viscosity measurement, as a quick method for the determination of the intrinsic viscosity, were compared with that obtained from [η] determined via the Huggins equation. The effect of molecular weights of the blend components and the polymer structure on the extent of compatibility was studied. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1471–1482, 1998     

A small-angle neutron scattering study on poly(ethylene oxide) crystals

Small-angle neutron scattering measurements were made on poly(ethylene oxide) (PEO) crystallized from the melt. Samples with the deuterated species (DPEO) as a matrix present distinct Bragg peaks from which the lamella spacings can be determined. As a result of strong void-scattering, quantitative analysis of the low-angle regime of these scattering curves is not possible. Samples with the protonous species as a matrix, for which void-scattering is expected to be negligibly small, present unusual scattering curves indicating that they consist of two components, i.e. the intramolecular and intermolecular interference terms. A quantitative analysis of these curves indicates: (1) the solute DPEO molecules are embedded in the crystalline structure of the matrix, assuming rod-like conformations but (2) forming essentially homogeneous aggregates of a few to tens of the DPEO molecules, depending on the crystallization temperature and the DPEO concentration; (3) the DPEO molecules or aggregates are distributed in space in a non-random manner that corresponds to the presence of inhomogeneous ‘domains’ having root-mean-square radii of about 250 Å, and each containing about 100 DPEO molecules.     

Conformation of poly(ethylene oxide) in the solid state,melt and solution measured by Raman scattering

The Raman spectrum of poly(ethylene oxide) (PEO) $\text{M}\text{?}{}_{\mathrm{w}}\text{= 3 × 10}{}^6$ and 6 × 10³ has been measured in bulk as a function of temperature and in aqueous and chloroform solution as a function of solvent concentration. The spectral features are assigned to particular isomeric configurations and the changes on melting are found to be consistent with a helix-coil transition. In both solvents the ordered nature of the polymer is largely lost at a critical concentration, approximately 50% by weight; residual ordering in dilute aqueous solution is lost and the random coil configuration attained only above the melting temperature. The wavenumber change of the 862 cm^?1 mode as a function of water concentration showed formation of a complex involving three water molecules and was consistent with a simple H-bonding model. The differences between the spectra in the two solvents are explained by this H-bonding. The results are in general agreement with n.m.r. work.     

Heterobifunctional poly(ethylene oxide)

Summary Well-defined poly(ethylene oxide)s with a primary amino group at one end and a hydroxyl group at the other terminus were synthesized with new sila-protected amino functionality initiator, potassium N-[2-(2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentyl)-ethyl]methyl amide [1b]. 1b initiated an anionic polymerization of ethylene oxide (EO) to form a polymer (PEO) without any side reactions such as a cleavage reaction of protective group and a chain transfer reaction. The molecular weights of the PEO determined from GPC and MALDI TOF-MS spectrometry agreed well with those from end group analysis using ¹H and ¹³C NMR and TLC and also with the expected value from EO/initiator ratio. From these results, it was concluded that the polymers thus obtained had a primary amino group at one end and a hydroxy group at the other end and can be regarded as hetrobifunctional PEO.     

Crystallization of poly(ethylene oxide) in i-polypropylene–poly(ethylene oxide) blends

A two-stage stable system of isotactic polypropylene–poly(ethylene oxide) blend, in which poly(ethylene oxide) can be permanent either in molten or in crystallized states in the temperature range from 280 to 327 K, was described. The behavior of that blend was explained in terms of fractionated crystallization. A fine dispersion of poly(ethylene oxide) inclusions is required for efficient suppression of crystallization initiated by heterogeneous nuclei. The application of a thin film of polypropylene-poly(ethylene oxide) 9 : 1 blend obtained by quenching for multiuse erasable and rewritable carriers for visible information has been demonstrated. The same sample exhibits different dynamic mechanical properties when poly(ethylene oxide) inclusions are molten or crystallized. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2047–2057, 1997     

Graft copolymers with poly(ethylene oxide) segments

Graft copolymers containing poly(ethylene oxide) as side chains attached to the backbone have attracted significant interest because of their unique properties. They have expanded a class of materials important for science and biomedicine. This review article describes a variety of synthetic procedures, i.e. directly by the macromonomer method or by the ‘grafting from’ technique as well as indirect routes via a polymeric precursor. The uses of these graft copolymers in numerous applications are presented to show their versatile nature and their potential. Copyright © 2007 Society of Chemical Industry     

Crosslinked poly(ethylene oxide) hydrogels

Poly(ethylene oxide) with a molecular weight of 2,000,000 was crosslinked by a difunctional peroxide in the molten state. We determined the molecular weight between crosslinks by swelling the samples with deionized water and by indentation and dynamic mechanical analysis. Results were compared with the calculated optimum molecular weight between crosslinks. Fair agreement was obtained between the experimental methods. However, the efficiency of peroxide‐induced crosslinking was very low. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1451–1455, 2003     

Block polymers from poly(ethylene oxide) and styrene

Block copolymers containing poly(ethylene oxide) and polystyrene segments were synthesised via chemical reactions. A step-wise procedure was first employed to prepare peroxycarbamates which were later used to initiate free radical polymerization of styrene at elevated temperatures. In some runs the polymerization temperature and time were programmed. Styrene contents, molecular weights, elastic modulus—temperature relationships, impact strengths and stress—strain behaviour of the copolymers were determined.     

X-ray low-angle scattering from oriented poly(ethylene terephthalate) films

Low-angle x-ray scattering data are used to deduce the morphology of oriented polymeric films. Generally, the structural models proposed to explain these patterns have been extrapolations of observations made from solution-grown polymer single crystals or from highly crystalline bulk polymers. These models and explanations may not be applicable broadly to oriented systems having only modest amounts of crystallinity or to those generated from precursor states that are grossly different. Poly(ethylene terephthalate) (PET) was chosen as a model polymer system for study. A systematic series of uniaxially and biaxially deformed films were produced from this polymer, made from the initially glassy or crystalline states. The low-angle x-ray scattering patterns generated from these films were studied as a function of (a) the sequence of deformation, (b) the precursor structure, (c) molecular orientation, and (d) the direction of observation. Optical diffraction and model structures were used to aid in the interpretation of the morphology produced. At least three different-sized domains are developed upon deformation, ranging from that of the unit cell (about 10 Å) to large laminar domains of average size 2,000 Å × 10,000 Å. This structure is shown to be substantially different from that developed in an oriented polyethylene film.     

Solvation of ion pairs with poly(ethylene oxide)

Summary Solvation of ion pairs of the alcoxide type with poly(ethylene oxide) (PEO) has been studied by optical spectroscopy. Values of binding constants 200–400 l/mol indicate a sufficiently effective ion-pair cation solvation. Being cross-linked PEO preserves its ability to bind and localize ion pairs.     

Toughening of polypropylene with crystallizable poly(ethylene oxide)

A crystallizable polymer, poly(ethylene oxide) (PEO), was used as new modifier to tailor the toughness of isotactic polypropylene (iPP). An optimum performance was achieved at a medium PEO content of 15 wt% where the toughness was enhanced by 300%, while the strength only decreased slightly. To elucidate the origin of toughening in the iPP/PEO blends, various crystallographic and morphological experiments including X‐ray diffraction, electron microscopy and calorimetry were adopted to explore the dependences of polymorphic composition and crystallized morphology on PEO content. When the PEO content is less than 15 wt%, the dispersed PEO cannot crystallize, and these non‐crystalline PEO microspheres are embedded in both α‐ and β‐form iPP spherulites, which is mainly responsible for the toughening. In contrast, when the PEO content is higher than 15 wt%, the PEO phase becomes crystallizable, and significant phase segregation takes place, resulting in a marked deterioration in mechanical properties. Copyright © 2011 Society of Chemical Industry     

含聚环氧乙烷链段梳形结构聚(异戊二烯-g-苯乙烯)的合成与表征

以聚苯乙烯(PS)大分子单体和异戊二烯为共聚单体,四氢呋喃为调节剂,正丁基锂为引发剂,三异丁基铝为助引发剂,脂肪族缩水甘油醚为官能化改性剂,采用一锅法经活性负离子共聚合制得以聚异戊二烯为主链、PS为规整侧链,且末端含星形聚环氧乙烷链段的极性化梳形聚(异戊二烯-g-苯乙烯-s-环氧乙烷)(PI-g-PS-s-PEO),利用凝胶渗透色谱仪、傅里叶变换红外光谱仪、差示扫描量热仪等对所制备的PI-g-PS-s-PEO进行了表征,并考察了PI-g-PS-s-PEO中聚环氧乙烷链段(PEO)质量分数(w_PEO)的影响因素。结果表明,产物具有分子结构可设计、分子量分布窄等优点。此外,PS大分子单体分子量对w_PEO无影响,减小缩水甘油醚分子量、增加其用量及延长封端反应时间均可提高w_PEO,且w_PEO在0.1%～1.8%可调。     

Electrospinning of sodium alginate with poly(ethylene oxide)

Another natural biopolymer, sodium alginate, has been electrospun from aqueous solution by blending with a non-toxic, biocompatible, synthetic polymer poly(ethylene oxide) (PEO). The interaction between sodium alginate and PEO has been evidenced by FTIR and conductivity change, which is thought to be the main reason for the successful electrospinning. The solution properties of sodium alginate/PEO blends have been measured, including viscosity, conductivity and surface tension. The morphology and mechanical properties of the electrospun mats have been investigated. Smooth fibers with diameters around 250 nm are obtained from 3% solutions of varied alginate/PEO proportions ranging from 1:1 to 0:1. Tensile strength around 4 MPa is found with smooth fiber mats. The anti-water property of the electrospun mats has been improved by a combination of hexamethylene diisocyanate and aqueous calcium chloride cross-linkings.     

Crystallization of block poly(ethylene oxide)

Urethane linked block polymers of poly(ethylene oxide) have been prepared and fractionated. Samples having 1 to 20 blocks per molecule, with molecular weights ranging from 1500 to 67 000 g/mol, have been examined by a number of techniques (small-angle X-ray scattering, differential scanning calorimetry, dilatometry, optical microscopy) in order to determine their crystallinities, melting points and spherulite growth rates. For a series of fractions having an average block length of 34 oxyethylene units with a range of 3 to 20 blocks per molecule, we find that equilibrium melting points are practically independent of molecular weight ($\text{6000 <}\text{M}\text{?}{}_{\mathrm{W}}\text{< 40 000}$). Analysis of the temperature dependence of the spherulite growth rates of these fractions leads to the conclusion that the pre-exponential factor (G₀) is practically independent of molecular weight and that the end interfacial free energy (σ_e) increases with molecular weight. Analysis of the experimental results for series of fractions having average block lengths of 45 or of 90 oxyethylene units is complicated by chain folding in the crystalline lamellae.     

Static and dynamic light scattering studies of the crystallization of poly(ethylene oxide) from dilute solutions

We have monitored in situ the self-seeded crystallization of poly(ethylene oxide) from dilute toluene solutions by dynamic light scattering. In supercooled dilute solution, the radii (R) of the crystals grow linearly with time. the rate constant obtained from the slope of the plot R versus time depends on the temperature and the molecular weight of the polymer, both of which determine the degree of the supercooling. The maximum crystal size obtained from solutions of fixed concentration also depends on the temperature and the polymer molecular weight. It appears that crystal growth is limited because of molecular weight fractionation. Static light scattering from suspensions of stable crystals provides information on the crystal morphology. A comparison of experimental and theoretical particle scattering functions suggests that the crystals form short cylinders and that the crystal growth from the seeds is primarily two-dimensional. Some comparisons to melt crystallization are possible. The preparation and use of tiny seed crystals is critical to the success of these studies.     

Amphiphilic polysilane with poly(ethylene oxide) side chains

The synthesis of an amphiphilic polysilane with poly(ethylene oxide) grafted segments (PS-g-PEO) through the addition of an allyl-terminated poly(ethylene oxide) (AT-PEO) to poly[diphenylsilane-co-methyl(H) silane] (PSH) in a homogeneous system and using catalyst platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane is reported The process involves the activation of the polymer by microwave irradiation as a preliminary stage with the view to perform the subsequent addition stage at room temperature, when side reactions are prevented. The PS-g-PEO structure was characterized by NMR, FT-IR spectral analysis and GPC methods. The amphiphilic properties were estimated by comparison of the water sorption isotherms of the PS-g-PEO copolymer with those of the component segments. The core-shell micellization in water and the morphological aspects of the self-assembled structures were investigated by DLS and SEM. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A study of mixtures of poly(ethylene oxide) with polystyrene or poly(styrene-co-acrylic acid) by inverse gas chromatography and viscosimetry

Summary Systems of poly(ethylene oxide)/polystyrene and of poly(ethylene oxide)/poly(styrene-co-acrylic acid) of different ratios were studied by inverse gas chromatography using benzene and n-decane as molecule probes and by viscosimetry in tetrahydrofuran. The transition temperatures as shown in the retention diagrams and the interaction parameters as determined by inverse gas chromatography and by viscosimetry showed that whereas poly(ethylene oxide) is incompatible with polystyrene, the introduction of amounts of acrylic acid groups into polystyrene chains by free radical copolymerization led to compatible systems of the acidic copolymer with the poly(ethylene oxide).     

Preparation and characterization of poly(lactic acid)/poly(ethylene oxide) blend film: effects of poly(ethylene oxide) and poly(ethylene glycol) on the properties

Poly(lactic acid) (PLA) film plasticized with poly(ethylene oxide) (PEO) at various weight percentages (1–5 wt%) was prepared to improve the elongation, thus overcoming the inherent brittleness of the material. After optimization of the amount of PEO (4 wt%) through mechanical analysis, poly(ethylene glycol) (PEG), a well‐established plasticizer of PLA, was added (0.5–1.5 wt%) without hampering the transparency and tensile strength much, and again its amount was optimized (1 wt%). Neat PLA and PLA with the other components were solvent‐cast in the form of films using chloroform as a solvent. Improvement in elongation at break and reduction in tensile strength suggested a plasticizing effect of both PEO and PEG on PLA. Thermal and infrared data revealed that the addition of PEO induced β crystals in PLA. Scanning electron micrographs indicated a porous surface morphology of the blends. PEO alone in PLA exhibited the best optical clarity with higher percentage crystallinity, while PEG incorporation in PLA/PEO resulted in superior barrier properties. Also, the stability of the blends under a wide range of pH means prospective implementation of the films in packaging of food and non‐food‐grade products. © 2018 Society of Chemical Industry