Miscibility enhancement on the immiscible poly (vinyl pyrrolidone) and poly (ethyl methacrylate) with poly (vinyl phenol)

The miscibility behavior of ternary blends of poly (vinyl phenol) (PVPh)/poly (vinyl pyrrolidone) (PVP)/poly (ethyl methacrylate) (PEMA) was investigated mainly with calorimetry. PVPh is miscible with both PVP and PEMA on the basis of the single T_g observed over the entire composition range. FTIR was used to study the hydrogen bonding interaction between the hydroxyl group of PVPh and the carbonyl group of PVP and PEMA at various compositions. Furthermore, the addition of PVPh is able to enhance the miscibility of the immiscible PVP/PEMA and eventually transforms it into a miscible blend, especially when the ratio between PVP/PEMA is 3:1, probably because of favorable physical interaction. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1205–1213, 2006     

Nanostructured polymer blend formed from poly(N-vinylpyrrolidone) and end-functional polystyrene

Phase structures of blends of poly(N-vinylpyrrolidone) (PVP) with SO₃H terminated polystyrene (PSS) were investigated. The PVP-PSS blends were macroscopically homogeneous, although the blends of PVP with polystyrene (PS) showed macroscopic phase separation. The PVP-PSS blends, however, showed two glass transitions indicating existence of two phases. Small-angle X-ray scattering measurements revealed the PVP-PSS blends formed mesomorphically ordered morphologies which change with variation of blend composition. The nano-organized phase separation in the PVP-PSS blends was caused due to hydrogen bonding of the PVP with the terminal SO₃H group of the PSS and repulsive interaction between PVP and main chain of the PSS.     

Role of specific interactions on fiber formation in the electrospinning of poly(vinyl phenol)/poly(vinyl pyrrolidone) blend solutions

The minimum concentration (C_i) required for electrospinning polymeric fibers from solutions of mixtures of poly(vinyl phenol) and poly(vinyl pyrrolidone) has been experimentally determined for different blend compositions. This minimum concentration C_i has its lowest value when the polymers are mixed in a 1/1 molar ratio. This article shows different results that seem to indicate that the strong hydrogen bonding interactions between the two polymers and the corresponding higher apparent molecular weight cause the reduction of the C_i value. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel miscible poly(ethylene sebacate)/poly(4-vinyl phenol) blends: Miscibility, melting behavior and crystallization study

High molecular weight samples of the novel biodegradable polyester poly(ethylene sebacate) (PESeb) were synthesized. Miscible poly(ethylene sebacate)/poly(4-vinyl phenol) semicrystalline/amorphous blends were prepared by applying the solvent casting method. Miscibility was proved by the single composition dependent glass transition temperature over the entire composition range observed in DSC traces of the quenched blend samples and also by the melting point depression. The Flory-Huggins interaction parameter was found to be x₁₂ = −1.3. Also, FTIR spectra supported the hypothesis of intermolecular interactions due to hydrogen bonding. The crystallization of PESeb in blends was studied. As expected, isothermal crystallization rates decreased in the blends with increasing the PVPh content. The Lauritzen-Hoffman analysis was tested. The values of nucleation constant K_g did not show any substantial variation. The non-isothermal crystallization of the blends was also tested. It was found that the crystallization is retarded in the case of blends, compared to the neat PESeb.     

Transient currents in poly(vinyl alcohol)–poly(vinyl pyrrolidone) polymer blend films

Transient currents (charging and discharging currents) in poly(vinyl alcohol) (PVA)–poly(vinyl pyrrolidone) (PVP) polymer blend films were measured over the temperature range 30–150°C at field strengths of 2.32–23.2 × 10⁶ Vm^?1. Polymer films were prepared by the isothermal immersion technique. Activation energies were evaluated from quasi-steady-state currents. A single relaxation peak was observed both from isochronal currents and low frequency dielectric relaxation. Activation energies evaluated from these two methods are found to be in fairly good agreement. The polarization is considered to be due to space charge origin along with some contribution from dipolar groups. The maximum loss was observed in Sample I (PVA: PVP = 25:75), suggesting maximum heterogeneity in this blend ratio.     

Hydrogen bonding interactions and miscibility studies of poly(amide)/poly(vinyl pyrrolidone) blends containing mangiferin

Miscibility studies of amorphous poly(amide)/poly(vinyl pyrrolidone) (PA/PVP) blends containing a crystalline phytochemical called “mangiferin” have been carried out using differential scanning calorimetry, Fourier transformed infrared spectroscopy and polarized optical microscopy. The binary blends of PA/PVP prepared from dimethylsulfoxide solutions were found to be completely miscible showing a systematic movement of a single glass transition temperature over the entire composition range. The FTIR study indicated the occurrence of cross-hydrogen bonding interactions between PA and PVP, which may be responsible for complete miscibility of the PA/PVP pair. Moreover, cross-hydrogen bonding promotes miscibility in binary blends of PA/mangiferin and PVP/mangiferin. However, the addition of mangiferin to PA/PVP blends has resulted in liquid-liquid phase separation between PA/mangiferin and PVP/mangiferin phases due to the preferential affinity of mangiferin to PVP than to PA. With increasing mangiferin concentration, liquid-liquid phase segregations occur between PA + mangiferin and PVP + mangiferin phases in addition to the solid-liquid phase transition of mangiferin crystals. Lastly, a ternary morphology phase diagram of the PA/PVP/mangiferin blends was established, which exhibited various coexistence regions such as isotropic, liquid + liquid, liquid + crystal, liquid + liquid + crystal, and solid crystal regions.     

Effect of copolymer compositions on the miscibility behavior and specific interactions of poly(styrene-co-vinyl phenol)/poly(vinyl phenyl ketone) blends

Differential scanning calorimetry and one- and two-dimensional Fourier transform infrared (FTIR) spectroscopies have been used to investigate the miscibility of and specific interactions between poly(styrene-co-vinyl phenol) (PSOH) and poly(vinyl phenyl ketone) (PVPK) upon varying the vinyl phenol content of the PSOH copolymer. The FTIR spectra revealed that the phenol units of PVPh interact strongly with the CO groups of PVPK through intermolecular hydrogen bonding, and more weakly with the aromatic rings of PVPK through intermolecular π-π interactions. A miscibility window exists when the vinyl phenol fraction in the copolymer is greater than 20 mol% in the PSOH/PVPK blend system, as predicted using the Painter-Coleman association model.     

Miscibility studies on linseed oil epoxy blend with poly(methacrylic acid)

With the aim to utilize a vegetable oil epoxy, a product from a sustainable resource, for improving the properties of polymethacrylic acid (PMAA), the blends of the latter with the epoxy of linseed oil were prepared in solution by mechanical mixing of the requisite amounts of the two components in dimethylsulphoxide. Freestanding films of the blend were cast. The miscibility of the two components was investigated by viscosity, ultrasonic, and density measurements which showed that the two components were semicompatible in solution. The compatibility in solid phase was also examined by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM), which revealed that linseed oil epoxy (LOE) and PMAA were incompatible. The films of blend of all compositions were found to be sticky, which was caused by the oozing of LOE. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Effect of bisphenol A on the miscibility,phase morphology,and specific interaction in immiscible biodegradable poly(ε‐caprolactone)/poly(L‐lactide) blends

We have investigated the enhancement in miscibility, upon addition of bisphenol A (BPA) of immiscible binary biodegradable blends of poly(ε‐caprolactone) (PCL) and poly(L ‐lactide) (PLLA). That BPA is miscible with both PCL and PLLA was proven by the single value of T_g observed by differential scanning calorimetry (DSC) analyses over the entire range of compositions. At various compositions and temperatures, Fourier transform infrared spectroscopy confirmed that intermolecular hydrogen bonding existed between the hydroxyl group of BPA and the carbonyl groups of PCL and PLLA. The addition of BPA enhances the miscibility of the immiscible PCL/PLLA binary blend and transforms it into a miscible blend at room temperature when a sufficient quantity of the BPA is present. In addition, optical microscopy (OM) measurements of the phase morphologies of ternary BPA/PCL/PLLA blends at different temperatures indicated an upper critical solution temperature (UCST) phase diagram, since the ΔK effect became smaller at higher temperature (200°C) than at room temperature. An analysis of infrared spectra recorded at different temperatures correlated well with the OM analyses. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1146–1161, 2006     

Syntheses and specific interactions of poly(hydroxyethyl methacrylate-b-vinyl pyrrolidone) diblock copolymers and comparisons with their corresponding miscible blend systems

Combination of atom transfer radical and conventional free radical polymerizations has been successfully used to prepare poly(hydroxyethyl methacrylate-b-vinyl pyrrolidone) (PHEMA-b-PVP) copolymers with controlled molecular weight and low polydispersity (<1.4). The thermal behavior and specific interaction of PHEMA-b-PVP diblock copolymers and their corresponding PHEMA/PVP blends were characterized. The result shows that glass transition temperatures of diblock copolymers analysed by differential scanning calorimetry (DSC) are higher than those of the blends. Infrared and solid-state NMR spectroscopic analyses show that hydrogen-bonding interaction of hydroxyl-carbonyl groups of diblock copolymers was also greater than that of the blends. Measurement of the proton spin-lattice relaxation time in the rotating frame, , reveals that all diblock copolymers and blends possess one composition-dependent , indicating that both diblock copolymers and blends are homogeneous, which is consistent with the DSC analysis.     

Pervaporation separation of isopropanol–water mixtures using mixed matrix blend membranes of poly(vinyl alcohol)/poly(vinyl pyrrolidone) loaded with phosphomolybdic acid

Mixed matrix membranes of poly(vinyl alcohol) and poly(vinyl pyrrilidone) blends were prepared by loading with phosphomolybdic acid (PMA) and their pervaporation (PV) properties were investigated for the PV separation of isopropanol. Membrane performance shown a dependence on the extent of PMA loading. The 4 wt % PMA‐loaded blend membrane had the highest separation factor of 29991, which declined considerably at higher loading. The flux of 4 wt % PMA‐loaded membrane was lower than that of nascent blend membrane. Feed water composition and temperature influenced the PV performance. Solubility selectivity was higher than diffusion selectivity. Degree of swelling was smaller after PMA loading exhibiting better separation ability. The PV results were analyzed using the Flory‐Huggins theory and sorption was dominated by Langmuir's mode. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Sequence distribution affect the phase behavior and hydrogen bonding strength in blends of poly(vinylphenol-co-methyl methacrylate) with poly(ethylene oxide)

Experimental results indicate that the PEO was miscible with PVPh-r-PMMA copolymers as shown by the existence of single composition-dependent glass transition temperature over the entire compositions. However, the PVPh-b-PMMA copolymer with PEO shows a like closed loop phase-separated region in this copolymer/homopolymer blend system. Furthermore, FTIR reveals that at least three competing equilibrium are present in these blends; self-association (hydroxyl-hydroxyl), interassociation (hydroxyl-carbonyl) of PVPh-co-PMMA, and hydroxyl-ether interassociation between PVPh and PEO. Based on the Painter-Coleman Association Model (PCAM), a value for inter-association, K_C=300 is obtained in PVPh-b-PMMA/PEO blend system at room temperature. Although the relative ratio of interassociation equilibrium constant of PEO to PMMA is larger in PVPh-b-PMMA/PEO blend system, the PVPh-r-PMMA/PEO blend system has greater Δν and greater homogeneity at the molecular scale than the PVPh-b-PMMA/PEO blend system because of the ΔK effect.     

Miscibility of poly(acrylic acid)/poly(methyl vinyl ketone) blend and in vitro application as drug carrier system

A series of poly(acrylic acid)/poly(methyl vinyl ketone) (PAA/PMVK) blends with different compositions were prepared by the solvent casting method. The miscibility of this pair of polymers was investigated by differential scanning calorimetry(DSC), Fourier transform infra-red (FTIR) and X-Ray diffraction (XRD) techniques. An in-vitro cytotoxicity test of the drug-carrier system via MTT (3-(4,5-demethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay revealed no significant cytotoxic effects at concentrations up to 100 µg· ml^?1. The STX/PAA-50 drug carrier systems were also prepared by solvent casting of solutions containing the sulfamethoxazole (STX) used as drug model and PAA/PMVK blend in N.N-dimethylformamide then crosslinked with acidified ethylene glycol. The release dynamic of STX from the prepared hydrogels was investigated in which the diffusion through the polymer matrix, the enhancement of the water solubility of STX, the influence of the initial drug concentration, the pH of the medium, and the effect of the degree of swelling of the polymer matrix on the release dynamic was evaluated. According to the total gastrointestinal transit time estimated by Belzer, the estimate distribution of STX released in the different organs indicated that the performance is obtained with the drug – carrier-system containing equal ratios of polymer and 10 wt% of STX (STX-10/PAA-50).     

Miscibility of poly(2,6-dimethyl-1,4-phenylene oxide)/poly(vinyl pyrrolidone) blends

The miscibility of blends of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and poly(vinylpyrrolidone) (PVP) was studied by differential scanning calorimetry (DSC) through the analysis of the glass transition temperature Tg. The dependence of Tg with the annealing temperature was determined for PPO and PVP samples of different molecular weights. The phase diagrams for blends containing three different PVP samples were established. Blends of PPO and PVP were found to be miscible for composition lower than 30% and higher than 65% of PVP. A inmiscibility window between 30 and 65% of PVP is also described.     

Constructive modification of conducting polyaniline characteristics in unusual proportion through nanomaterial blend formation with the neutral polymer poly(vinyl pyrrolidone)

The present work reports an investigation on the modification of conducting polyaniline (PANI) characteristics favorably on blending with the neutral polymer, poly(vinyl pyrrolidone) (PVP) in a systematic variation of their molar ratios (aniline : PVP = 4 : 1, 2 : 1, 1 : 1, 1 : 2, and 1 : 3). Prepared by precipitation technique by conventional in situ chemical oxidative polymerization with ammonium peroxodisulfate in aqueous H₂SO₄ medium (pH 1.0), these materials have nanometer sizes (～ 50–200 nm) and, depending on the molar ratios, exhibit a distinct deviation in physicochemical characteristics from those of pristine PANI prepared in the identical condition. A gradual trend in characteristics is noticed in first three PANI–PVP blends, while an abnormal hike in conductivity, unusual spectral features in IR and UV–vis, hardened nature, and induction of characteristic morphology, crystallinity, and thermal stability are associated with the last two blends that have excess PVP. Thus a division of two sets of nanoblends, one set with less or equal content of PVP and another with excess of PVP, emerges. Evidently, PVP has a tuning effect on PANI through its dopant, supporting matrix and interpenetrating steric stabilizer acts in proportion quite unusual to its neutral nature. The study altogether brings to light a simple way of modification of PANI characteristics by conventional method of blend synthesis. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Studies on dielectric relaxation and ac conductivity of cellulose acetate hydrogen phthalate–poly (vinyl pyrrolidone) blend

The dielectric constant, dielectric loss, and ac conductivity of polyblends of cellulose acetate hydrogen phthalate (CAP) and poly (vinyl pyrrolidone) (PVP) of different compositions were measured in the temperature range of 300–430 K and in the frequency range of 50 Hz–100 kHz. In the blends, the dielectric constant as well as the dielectric loss as a function of the temperature display a single peak corresponding to the glass transition temperature (T_g) in the region between the T_g values of the pure polymers. The T_g values observed agree well with those values obtained from DSC. Dielectric studies show that CAP forms a miscible blend with PVP. Ac conductivity values were calculated from the dielectric data and the conduction mechanism is discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1702–1708, 2002     

In vitro release study of diltiazem hydrochloride from poly(vinyl pyrrolidone)/sodium alginate blend microspheres

Polymeric blend microspheres of poly(vinyl pyrrolidone) (PVP) with sodium alginate (NaAlg) were prepared by cross‐linking with calcium ions and used to deliver a calcium channel blocker drug, diltiazem hydrochloride (DT). The prepared microspheres were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. Scanning electron microscopy confirmed the spherical nature of the particles. Preparation conditions for the microspheres were optimized by considering the percentage entrapment efficiency, particle size, and swelling capacity. Effects of variables such as PVP/NaAlg ratio, molecular weight of PVP, cross‐linker concentration, and drug/polymer ratio on the release of DT were discussed at two different pH values (1.2, 6.8) at 37°C. It was observed that DT release from the microspheres decreased with increasing molecular weight of PVP and extent of cross‐linking. However, DT release increased with increasing PVP content and drug/polymer ratio (d/p) of the blend microspheres. The highest DT release percentage was obtained as 99% for PVP/NaAlg ratio of 1/2 with d/p ratio of 1/2 at the end of 4 h. It was also observed from release results that DT delivery from the microspheres through the external medium are much higher at low pH (1.2) value than that of high pH (6.8) value. The drug release from the microspheres mostly followed Fickian transport. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Miscibility of biodegradable aliphatic polyester and poly(vinyl acetate) blends

We report miscibility behavior for synthetic biodegradable aliphatic polyester (BDP) and poly(vinyl acetate) (PVAc) blends by investigating their thermal, rheological, and mechanical properties. Two separate glass transition temperature peaks for the BDP/PVAc blends proved that these blend systems are immiscible. From the rheological measurement, the shear viscosity as a function of shear rate is observed to increase with increasing PVAc content in BDP/PVAc blends, since PVAc has a relatively high molecular weight compared to BDP. Moreover, BDP blends with 10 wt % PVAc have excellent mechanical properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1348–1352, 2000