Evolution of concentration fluctuation during phase separation of polystyrene/poly(vinyl methyl ether) blend in the presence of nanosilica

The influence of nanosilica on the concentration fluctuation of polystyrene/poly (vinyl methyl ether) (PS/PVME) mixtures was investigated during phase separation. The amplitude of concentration fluctuation was quantified by dielectric spectrums based on the idea of Lodge–Mcleish model and the linearized Cahn–Hilliard theory could describe the amplitude evolution of concentration fluctuation at the early stage of phase separation. Hydrophilic nanosilica A200 dispersed in PVME‐rich phase behaved an obvious inhibition effect on the concentration fluctuation of blend matrix, while hydrophobic nanosilica R974 dispersed in PS‐rich phase had little effect on the concentration fluctuation. The kinetics and amplitude evolution of concentration fluctuation during phase separation for PS/PVME/A200 nanocomposites were remarkably restrained due to the surface adsorption of PVME on A200. As the segmental dynamics of PVME and PS in homogeneous matrix was hardly influenced by A200 and R974, the enhanced miscibility and the significantly constrained flow relaxation of PVME chains might contribute to the retarded concentration fluctuation of PS/PVME/A200 nanocomposites. While the weak interaction between R974 and components of blend matrix and little effect of R974 on the molecular dynamics of PS chains may result in the weak retardation of concentration fluctuation for blend matrix. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1337–1349     

Photooxidation of blends of polystyrene and poly (vinyl methyl ether)

Photooxidation of blends of polystyrene and poly (vinyl methyl ether) was studied at 30°C. The oxygen uptake by PS was negligible but PVME oxidized readily. The induction period of oxidation of PVME was prolonged by the presence of PS. The steady state rate of oxidation of the blend was strongly influenced by the segmental mobility of the blend which also governed the kinetics and morphology of phase separation. The molecular weight of PVME decreased more slowly in the blend as PS content increased. It was believed that the reaction between PVME radicals and PS resulted in less reactive PS radicals which retarded oxidation. The PS radicals eventually underwent chain scission reactions.     

The effect of phase‐separated morphology on the rheological properties of polystyrene/poly(vinyl methyl ether) blend

The effect of phase‐separated morphology on the rheological properties of polystyrene/poly(vinyl methyl ether) (PS/PVME) blend was investigated by optical microscopy (OM), light scattering (LS) method, and rheology. The blend had a lower critical solution temperature (LCST) of 112°C obtained by turbidity experiment using LS at a heating rate of 1°C/h. Three different blend compositions (critical 30/70 PS/PVME by weight) and two off‐critical (50/50 and 10/90)) were prepared. The rheological properties of each composition were monitored with phase‐separation time after a temperature jump from a homogeneous state to the preset phase‐separation temperature. For the 30/70 and 50/50 blends, it was found that with phase‐separation time, the storage and loss moduli (G′ and G″) increased at shorter times due to the formation of co‐continuous structures resulting from spinodal decomposition. Under small oscillatory shearing, shear moduli gradually decreased with time at longer phase‐separation times due to the alignment of co‐continuous structures toward the flow direction, as verified by scanning electron microscopy. However, for the 10/90 PS/PVME blend, the rheological properties did not change with phase‐separation times. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 889–906, 1999     

Phase separation dynamics of a poly(vinyl methyl ether)/polystyrene (PVME/PS) blend studied by ultrafast differential scanning calorimetry

In this work, ultrafast differential scanning calorimetry (UFDSC) is used to study the dynamics of phase separation. Taking poly(vinyl methyl ether)/polystyrene (PVME/PS) blend as the example, we firstly obtained the phase diagram that has lower critical solution temperature (LCST), together with the glass transition temperature (T_g) of the homogeneous blend with different composition. Then, the dynamics of the phase separation of the PVME/PS blend with a mass ratio of 7:3 was studied in the time range from milliseconds to hours, by the virtue of small time and spatial resolution that UFDSC offers. The time dependence of the glass transition temperature (T_g) of PVME‐rich phase, shows a distinct change when the annealing temperature (T_a) changes from below to above 385 K. This corresponds to the transition from the nucleation and growth (NG) mechanism to the spinodal decomposition (SD) mechanism, as was verified by morphological and rheometric investigations. For the SD mechanism, the temperature‐dependent composition evolution in PVME‐rich domain was found to follow the Williams–Landel–Ferry (WLF) laws. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1357–1364     

Effect of shear flow on the phase‐separation behavior in a blend of polystyrene and polyvinyl methyl ether

The phase behavior and phase‐separation dynamics of polystyrene/polyvinyl methyl ether (PS/PVME) blend with a critical composition of 70 vol % PVME were examined with a light scattering technique under a shear‐rate range of 0.1–40 s^?1. If the shear rates were less than 8 s^?1 and the starting temperatures of the measurement were 343 and 383 K, respectively, two cloud points were observed, whereas after the shear rate was higher than 8 s^?1, only one cloud point existed, 20 K higher than that of the static state of the blend. Investigation of the phase‐separation dynamics at 443 K suggested that in the vorticity direction the phase‐separation behavior at the early stage and the later stage can be explained by Cahn–Hilliard linearized theory and the exponent growth law, respectively. Phase separation occurs after a shearing time, which was called a delay time τ_d. The delayed time τ_d, the apparent diffusion coefficient, and the exponent term of the blend show strong dependence on shear rates. A theoretical prediction of the phase behavior of PS/PVME under a shear flow field by introducing an elastic energy term into Flory's equation‐of‐state theory was made, and the prediction was consistent with the experimental results. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 661–669, 2003     

Phase separation of polymer mixtures induced by polarization‐selective chemical reactions: spatial symmetry breaking and mode selection

Phase separation of polystyrene/poly (vinyl methyl ether) (PS/PVME) blends was induced and controlled by irradiation with linearly polarized light. The PS component was made photosensitive by chemically labeled with either anthracene or trans‐stilbene. The former was used to crosslink the PS component whereas the latter induces phase separation by changing polymer segmental volumes. The phase separation and reaction kinetics were observed and discussed in terms of mode‐selection process.     

Phase Separation,Wetting and Dewetting in PS/PVME Blend Thin Films: Dependence on Film Thickness and Composition Ratio

The effects of film thickness and composition ratio on the morphology evolution of polystyrene (PS)/poly(vinyl methyl ether) (PVME) blend thin films were investigated. Diverse morphology evolutions including droplet-matrix structure, hole emergence, bicontinuous structure formation, percolation-to-droplet transition could be observed under annealing in two-phase region, depending on film thickness and composition ratio. The mechanism for these morphology variations was related to the complex effects of phase separation, dewetting and preferential wetting. The comparison between the thickness of bottom PVME layer and the twice of gyration radius 2R_g(PVME) played a dominant role in morphology control. Only when the PS/PVME film had specific film thickness and compositional symmetry, phase separation and dewetting could happen in sequence.     

Photochemistry of iminium salts : Electron transfer mechanisms for singlet quenching and photoaddition of n-electron donating alcohols and ethers

Several aspects of past and current studies in the area of iminium salt photochemistry are discussed. Investigations of olefin-iminium salt photoaddition and photocyclization reactions are reviewed and conclusions about electron-transfer pathways for fluorescence quenching and reaction are discussed. The results of recent studies of alcohol and ether photoaddition to 2-phenyl-1-pyrrolinium salts are presented. These C-C bond forming processes occur in moderate yields to produce β-amino alcohol or ether products. In addition, alcohols and ethers serve as efficient quenchers of pyrrolinium salt fluorescence. Rate constants for quenching appear to be dependent upon both the oxidation potential of the alcohols and ethers and the availability of C-H bond α to oxygen. This data along with deuterium isotope effects on quenching combine to suggest a common mechanism for both fluorescence quenching and photoaddition. The nature of this mechanism is tested using the comparative quenching effeciencies of the tertiary alcohols t-butyl alcohol and 1,2,2-trimethyl-1-cyclopropanol. The latter alcohol having a weak C-C bond adjacent to the hydroxyl function quenches the fluorescence of 2-phenyl-1-pyrrolium salts at a rate two orders of magnitude greater than for t-butyl alcohol. The observations made are interpreted in terms of a sequential electron-proton transfer mechanism for quenching and photoaddition. Lastly, the relationship of iminium salt photochemical studies to other investigations of electron-transfer photochemistry is discussed.     

Self-assembly via a complex phase transition in mixtures of polystyrene-block -polybutadiene block copolymer and poly(methyl vinyl ether)

The self-assembly of a binary mixture of polystyreneblock-polybutadiene (SB) and poly(methyl vinyl ether) (PVME) was studied by transmission electron microscopy and time-resolved light scattering. The self-assembly studied involved first microphase separation, in which a microdomain structure composed of polybutadiene block chains (PB) was formed in a matrix composed of polystyrene block chains (PS) and PVME homopolymers, and subsequently macrophase separation of the PVME from the microdomain phase of SB. The microphase separation was induced in a film preparation process using a solution cast method at room temperature. The macrophase separation was induced by rapidly heating the film specimens to above a critical temperature where PVME and PS undergo spinodal decomposition (SD). This complex phase transition, involving microphase separation followed by macrophase separation, was found to generate a superlattice structure (or a modulated structure) with two characteristic spacings: A_macro associated with the SD and A_micro associated with the microphase separation, both being generally time-dependent. The growth of the “macrodomains” was found to be pinned at A_macro ˜ 840 nm due to the elastic effect of the microdomain structure. The microdomain structure with A_micro ˜ 57 nm was found to undergo a morphological transition (a transition between two ordered phases of block copolymers) as a consequence of the local composition change of the two polymers induced by the SD.     

High-temperature fourier transform infrared study of polystyrene/poly(vinyl methyl ether) blends

Fourier transform infrared (FTIR) studies of polystyrene (PS)/poly(vinyl methyl ether) (PVME) miscible blends as a function of temperature are presented. Below the lower critical solution temperature (LCST) little change is observed in the interaction spectrum obtained via digital subtraction techniques. Once above the LCST, the magnitude of the interaction spectrum decreases as a result of the phase separation process. Comparison of the behavior of the ether C? O stretching band in the reference PVME and in the blends has yielded a lower limit estimate for the interaction energy of about 0.15 kcal/mol.     

Immiscibility,upper critical solution temperature,and miscibility in blends of poly(vinyl ether)s with polyacrylics: Effects of pendant groups

Various phase behavior of blends of poly(vinyl ether)s with homologous acrylic polymers (polymethacrylates or polyacrylates) were examined using differential scanning calorimetry, optical microscopy (OM), and Fourier‐transformed infrared spectroscopy. Effects of varying the pendant groups of either of constituent polymers on the phase behavior of the blends were analyzed. A series of interestingly different phase behavior in the blends has been revealed in that as the pendant group in the acrylic polymer series gets longer, polymethacrylate/poly(vinyl methyl ether) (PVME) blends exhibit immiscibility, upper critical solution temperature (UCST), and miscibility, respectively. This study found that the true phase behavior of poly(propyl methacrylate)/PVME [and poly(isopropyl methacrylate)/PVME)] blend systems, though immiscible at ambient, actually displayed a rare UCST upon heating to higher temperatures. Similarly, as the methyl pendant group in PVE is lengthened to ethyl (i.e., PVME replaced by PVEE), phase behavior of its blends with series of polymethacrylates or polyacrylates changes correspondingly. Analyses and quantitative comparisons on four series of blends of PVE/acrylic polymer were performed to thoroughly understand the effects of pendant groups in either polyethers (PVE's) or acrylic polymers on the phase behavior of the blends of these two constituents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1521–1534, 2007     

Phase separation in polystyrene/poly (vinyl methyl ether) blend revealed by two-dimensional correlation resonance light scattering spectroscopy

Two-dimensional (2D) correlation resonance light scattering (RLS) spectroscopy has been successfully applied to investigate phase separation of polystyrene (PS)/poly (vinyl methyl ether) (PVME) film by using a conventional spectrofluorimeter. 2D synchronous correlation RLS spectrum indicates that the RLS peak intensity drastically increases with a rise in temperature due to aggregation of chromophores (i.e. phenyl rings) in PS particles in the course of phase separation. In addition, as concluded by 2D asynchronous correlation RLS spectrum, RLS has higher sensitivity than conventional light scattering. For RLS, the closer to the absorption band, the more sensitive it is to the aggregation during phase separation. By means of moving-window two-dimensional (MW2D) correlation spectrum based on autocorrelation calculations, the cloud point (370 K) was determined, which is in good agreement with the literature. On the other hand, time evolution of RLS intensity at various temperatures distinctly shows that phase separation of PS/PVME film involves two mechanisms, i.e. spinodal decomposition (SD) and nucleation and growth (NG). Accordingly, 2D correlation RLS proves to be a very simple and sensitive method to monitor phase separation in polymer blends and might supplement the existing characterization tools.     

Thermally induced phase separation of polystyrene-poly(vinyl methyl ether) mixtures

Past differential scanning calorimetry and dielectric relaxation measurements have established that polystyrene (PS)-poly(vinyl methyl ether) (PVME) mixtures exhibit a degree of compatibility when cast from toluene, whereas they are incompatible when cast from chloroform or trichloroethylene. The present study reports that toluene-cast mixtures can be phase-separated by thermal treatment at temperatures exceeding 125°C. This is true for samples containing 20–80 wt-% PS. The temperature of phase separation varies with heating rate; isothermal heating times needed to cause phase separation increase rapidly as the temperature approaches 125°C. Reversibility of the phase separation process depends upon such factors as cooling rate, annealing time, treatment temperature, and thermal history. By annealing and/or slow cooling, all thermally phase-separated mixtures have been brought back to their original state of compatibility. That is, there is no evidence for true irreversiblity of phase separation in thermally treated samples. Quench-cooled samples remain phase-separated indefinitely at room temperature, but this is attributed to rapid cooling below the glass transition of the PS. Chloroform-cast and trichloroethylene-cast mixtures have not been brought to a compatible state by thermal treatment, even after lengthy annealing and slow cooling steps.     

Hydrophilic membranes based on poly(vinyl methyl ether-crosslinked-polystyrene) semi-interpenetrating networks

Microporous membranes were prepared from poly(vinyl methyl ether - crosslinked-polystyrene) (PVME-cross-PS) semi-IPN's by extraction of poly(vinyl methyl ether) (PVME) with water. Membrane morphology and properties are fixed during the process of swelling, phase separation, PVME extraction and vitrification which occurs upon immersing the samples in water. The membranes are characterized by swelling (water uptake), the relative amounts of free and bound water, and their permselectivity towards KCI solution.     

Anisotropic phase separation of polymer blends induced by polarization-selective photoisomerization

Anisotropic phase separation of polystyrene/poly(vinyl methyl ether) (PS/PVME) blends was induced by photoisomerization of trans-stilbene moieties labeled on the PS chains (abbreviated hereafter as PSS chains) using linearly polarized light. As temperature increases, the anisotropy becomes weaker and eventually disappears at 10°C above the glass transition of the PSS component. It was concluded that the elastic stress associated with the spatial distribution of the reaction is responsible for this morphological anisotropy.     

Molecular dynamics and phase behavior of polystyrene/poly(vinyl methyl ether) blend in the presence of nanosilica

The variation of phase morphology, critical temperature of demixing, and molecular dynamics for polystyrene/poly(vinyl methyl ether)(PS/PVME) blends induced by hydrophilic nanosilica(A200) or hydrophobic nanosilica(R974) was investigated. With the phase separation of blend matrix, A200 migrated into PVME-rich phase due to strong interaction between A200 and PVME, while R974 moved into PS-rich phase. The thermodynamic miscibility and concentration fluctuation during phase separation of blend matrix were remarkably retarded by A200 nanoparticles due to the surface adsorption of PVME on A200, verified by the correlation length ξ near the critical region from rheological measurement and the weakened increment of reversing heat capacity(ΔC_p) during glass transition via modulated differential scanning calorimetry(MDSC). The restricted chain diffusion induced by nanosilica still occurred despite no influence of A200 and R974 on the segmental dynamics of homogenous blend matrix. The interactions between nanosilica and polymer components could restrict the terminal relaxation of blend matrix and further manipulate their phase behavior.     

苯乙烯-丁二烯-苯乙烯/聚乙烯基甲基醚共混体系相容性的FT-IR及DSC研究

嵌段高聚物、均聚物共混体系相容性是近年来研究的热点。本工作以光学显微镜、DSC、FT-IR为手段,研究了三嵌段高聚物苯乙烯-丁二烯-苯乙烯(SBS);SBS-48、SBS-30,SBS-28与聚乙烯基甲基醚共混体系的相容性。DSC结果表明,随SBS中PS含量的升高,体系相容性变好,PS段分子量增大,也有助于体系相容。FT-IR结果表明PVME中COCH_3在1100cm~(-1)附近呈现的双峰的相对强度对体系的相容性十分敏感,而由于苯环C—H振动产生的698cm~(-1)峰位却不象PS/PVME体系那样随相容性的改变而有显著的改变。总而言之,嵌段高聚物SBS/均聚物PVME共混体系中,体系的相容性依赖于嵌段高聚物在体系中的组份含量及嵌段高聚物中PS的重量百分含量,PS段分子量的大小对体系相容性也有影响。     

Chemiluminescence study of PS–PVME compatible mixtures

The oxidation of polystyrene (PS), poly(vinyl methyl ether) (PVME), and their mixtures has been studied by the chemiluminescence method. It was found that luminescence versus temperature curves had sharp inflections that shifted to higher temperatures with increasing PS content of the blends. A linear relationship was obtained between inflection temperatures and onsets of oxidation exotherms as measured by calorimetry. The inflection points for the mixtures also correlated linearly with the temperatures of thermally induced phase separation     

Excited-State Intramolecular Proton Transfer Dyes with Dual-State Emission Properties: Concept,Examples and Applications

Dual-state emissive (DSE) fluorophores are organic dyes displaying fluorescence emission both in dilute and concentrated solution and in the solid-state, as amorphous, single crystal, polycrystalline samples or thin films. This comes in contrast to the vast majority of organic fluorescent dyes which typically show intense fluorescence in solution but are quenched in concentrated media and in the solid-state owing to π-stacking interactions; a well-known phenomenon called aggregation-caused quenching (ACQ). On the contrary, molecular rotors with a significant number of free rotations have been engineered to show quenched emission in solution but strong fluorescence in the aggregated-state thanks to restriction of the intramolecular motions. This is the concept of aggregation-induced emission (AIE). DSE fluorophores have been far less explored despite the fact that they are at the crossroad of ACQ and AIE phenomena and allow targeting applications both in solution (bio-conjugation, sensing, imaging) and solid-state (organic electronics, data encryption, lasing, luminescent displays). Excited-State Intramolecular Proton Transfer (ESIPT) fluorescence is particularly suitable to engineer DSE dyes. Indeed, ESIPT fluorescence, which relies on a phototautomerism between normal and tautomeric species, is characterized by a strong emission in the solid-state along with a large Stokes’ shift, an enhanced photostability and a strong sensitivity to the close environment, a feature prone to be used in bio-sensing. A drawback that needs to be overcome is their weak emission intensity in solution, owing to detrimental molecular motions in the excited-state. Several strategies have been proposed in that regard. In the past few years, a growing number of examples of DSE-ESIPT dyes have indeed emerged in the literature, enriching the database of such attractive dyes. This review aims at a brief but concise overview on the exploitation of ESIPT luminescence for the optimization of DSE dyes properties. In that perspective, a synergistic approach between organic synthesis, fluorescence spectroscopy and ab initio calculations has proven to be an efficient tool for the construction and optimization of DSE-ESIPT fluorophores.     

Application of Ultrasonic Attenuation Measurements in the Studies on Macromolecular Conformational Behaviors

——Phase Behavior of the Aqueous Solution of Poly(vinyl methyl ether) Sensitive to Temperature and the Modification of the Behavior by Using Poly(acrylic acid) The phase behavior of the aqueous solution of poly(vinyl methyl ether) (PVME) sensitive to temperature and the modification of the behavior by using poly(acrylic acid) (PAA) have been studied by ultrasonic attenuation measurements and fluorescence probe techniques. It has been observed that PVME solution is transparent at room temperature and becomes turbid upon heating. The solution turns clear again as soon as the temperature is decreased to room temperature. The heating and cooling process can be repeated for many times. The phase behavior of the solution sensitive to temperature is attributed to the conformational changes of the polymer. PVME may adopt an open coil conformation at room temperature. With this conformation, the polymer is well miscible with the solvent, water, and thereby the system is a real solution. The polymer may adopt a compact coil conformation when the temperature is higher than a specific value, which is called the LCST (the lower critical solution temperature) of PVME. In this case, the polymer tangles to each other and forms various aggregates, which can scatter incident light and ultrasonic waves greatly, resulting in the phase separation. Introduction of PAA decreases the temperature sensitivity of the phase behavior of the polymer. The nature of the inhibition is attributed to the complexation of PAA with PVME and the strong hydrophilicity of PAA. Results from fluorescence probe studies are in accordance with those from ultrasonic attenuation measurements, indicating again that the ultrasonic attenuation method can be successfully used for the qualitative studies of polymer conformations and complexation between polymers.