A Viscometric Study of the Miscibility Behaviour of Poly(N-Vinyl Pyrrolidone) Blends

The miscibility behaviour of blends of poly(N-vinyl pyrrolidone) (PVP) with poly(vinyl chloride) (PVC), poly(vinyl acetate) (PVAc) and vinyl chloride–vinyl acetate (VCVAc) copolymer has been investigated on the basis of a viscometric approach. PVP is found to be miscible with PVC over the entire composition range, as is evident from the high values observed for the intrinsic viscosity of transfer. This is further supported by the single glass transition temperature observed in differential scanning calorimetry studies of the blend films. Blends of PVP with VCVAc copolymer exhibit microphase separation which is shown clearly in the scanning electron micrographs of the films. PVAc/PVP blends show interaction only at low PVAc contents, but in general are immiscible. © of SCI.     

Miscibility enhancement on the immiscible binary blend of poly(vinyl acetate) and poly(vinyl pyrrolidone) with bisphenol A

The miscibility behavior and hydrogen bonding of ternary blends of bisphenol A (BPA)/poly(vinyl acetate) (PVAc)/poly(vinyl pyrrolidone) (PVP) were investigated by using differential scanning calorimetry and Fourier transform infrared spectroscopy (FTIR). The BPA is miscible with both PVAc and PVP based on the observed single T_g over the entire composition range. FTIR was used to study the hydrogen-bonding interaction between the hydroxyl group of BPA and the carbonyl group of PVAc and PVP at various compositions. Furthermore, the addition of BPA is able to enhance the miscibility of the immiscible PVAc/PVP binary blend and eventually transforms into miscible blend with single T_g, when a sufficiently quantity of the BPA is present due to the significant Δχ and the ΔK effect.     

Polymer nanocomposites containing carbon nanotubes and miscible polymer blends based on poly[ethylene‐co‐(acrylic acid)]

Four binary polymer blends containing poly [ethylene‐co‐(acrylic acid)] (PEAA) as one component, and poly(4‐vinyl phenol‐co‐2‐hydroxy ethyl methacrylate) (P4VPh‐co‐2HEMA) or poly(2‐ethyl‐2‐oxazoline) (PEOx) or poly(vinyl acetate‐co‐vinyl alcohol) (PVAc‐co‐VA) or poly (vinylpyrrolidone‐co‐vinyl acetate) (PVP‐co‐VAc) as the other component were prepared and used as a matrix of a series of composite materials. These binary mixtures were either partially or completely miscible within the composition range studied and were characterized by differential scanning calorimetry (DSC) and Fourier transformed infrared spectroscopy (FTIR). Carbon nanotubes (CNTs) were prepared by a thermal treatment of polyester synthesized through the chemical reaction between ethylene glycol and citric acid over an alumina boat. High resolution transmission electron microscopy (HRTEM) was used to characterize the synthesized CNTs. Films of composite materials containing CNTs were obtained after evaporation of the solvent used to prepare solutions of the four types of binary polymer blends. Young's moduli of the composites were obtained by thermomechanical analysis at room temperature. Only one glass transition temperature was detected for several compositions on both binary blends and the composite material matrices. Evidence of hydrogen bond formation was recorded for both miscible blends and composite materials. The degree of crystallinity and Young's moduli of the CNT‐polymer composites increased compared to the single polymer blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Effect of dehydrochlorination of PVC on miscibility and phase separation of binary and ternary blends of poly(vinyl chloride), poly(ethylene-co-vinyl acetate) and poly(styrene-co-acrylonitrile)

The enhancement of miscibility at the lower critical solution temperature (LCST) of the blends poly(vinyl chloride)/poly(ethylene-co-vinyl acetate) (PVC/EVA), poly(vinyl chloride)/poly(styrene-co-acrylonitrile) (PVC/SAN) and poly(vinyl chloride)/poly(ethylene-co-vinyl acetate)/poly(styrene-co-acrylonitrile) (PVC/EVA/SAN) was observed at the micron level. Such miscibility is attributed to the dehydrochlorination and formation of hydrogen bonds between blend components. However, macrolevel immiscibility of these blends heated to the LCST was observed. Such microdomain compatibility of these blends gives a synergistic character. Brittle-type failure observed for LCST samples testifies to the synergism in treated blends. ©1997 SCI     

Miscibility and complexation behavior of poly(cyanomethyl methacrylate) and poly(2-cyanoethyl methacrylate) with tertiary amide polymers

The miscibility and complexation behavior of poly(cyanomethyl methacrylate) (PCYMMA) and poly(2-cyanoethyl methacrylate) (PCYEMA) with various tertiary amide polymers was studied. PCYMMA and PCYEMA form interpolymer complexes with poly(N-methyl-N-vinylacetamide) (PMVAc) or poly(N-vinyl-2-pyrrolidone) (PVP) in tetrahydrofuran (THF) solutions. PCYMMA also forms complexes with poly(N,N-dimethylacrylamide) (PDMA) in THF solutions. However, PCYEMA does not form complexes with PDMA in THF solutions, but the THF-cast blends are miscible over the entire composition range. Both PCYMMA and PCYEMA do not form complexes with poly(2-ethyl-2-oxazoline) (PEOx) in THF solutions and are only miscible with PEOx when the blend contains greater than 60 wt % PCYMMA or 80 wt % PCYEMA. On the other hand, both PCYMMA and PCYEMA do not form complexes with PMVAc, PVP, or PDMA in N,N-dimethylformamide (DMF) solutions. The compositions of the complexes consist of simple mole ratios of the component polymers, and the glass-transition temperatures of the complexes are higher than those of the DMF-cast blends of similar compositions. Fourier-transform infrared spectroscopy provides further evidence on the miscibility behavior through changes in the amide carbonyl absorption bands of each tertiary amide polymer in the blends as well as in the cyano absorption band of PCYEMA. © 1995 John Wiley & Sons, Inc.     

Competitive hydrogen bonding mechanisms underlying phase behavior of triple poly(N‐vinyl pyrrolidone)–poly(ethylene glycol)–poly(methacrylic acid‐co‐ethylacrylate) blends

Differential scanning calorimetry (DSC) of triple blends of high molecular weight poly(N‐vinyl pyrrolidone) (PVP) with oligomeric poly(ethylene glycol) (PEG) of molecular weight 400 g/mol and copolymer of methacrylic acid with ethylacrylate (PMAA‐co‐EA) demonstrates partial miscibility of polymer components, which is due to formation of interpolymer hydrogen bonds (reversible crosslinking). Because both PVP and PMAA‐co‐EA are amorphous polymers and PEG exhibits crystalline phase, the DSC examination is informative on the phase state of PEG in the triple blends and reveals a strong competition between PEG and PMAA‐co‐EA for interaction with PVP. The hydrogen bonding in the triple PVP–PEG–PMAA‐co‐EA blends has been established with FTIR Spectroscopy. To evaluate the relative strengths of hydrogen bonded complexes in PVP–PEG–PMAA‐co‐EA blends, quantum‐chemical calculations were performed. According to this analysis, the energy of H‐bonding has been found to diminish in the order: PVP–PMAA‐co‐EA–PEG(OH) > PVP–(OH)PEG(OH)–PVP > PVP–H₂O > PVP–PEG(OH) > PMAA‐co‐EA–PEG(? O? ) > PVP–PMAA‐co‐EA > PMAA‐co‐EA–PEG(OH). Thus, most stable complexes are the triple PVP–PMAA‐co‐EA–PEG(OH) complex and the complex wherein comparatively short PEG chains form simultaneously two hydrogen bonds to PVP carbonyl groups through both terminal OH‐groups, acting as H‐bonding crosslinks between longer PVP backbones. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Blend of chitosan acetate salt with poly(N-vinyl-2-pyrrolidone): Interaction between chain-chain

SUMMARY: Clear blends of chitosan acetate salt with poly (N-vinyl-2-pyrrolidone) (PVP) made from aqueous solutions look to be miscible on appearance. IR spectra investigated the carbonyl-hydroxyl hydrogen bonding between chain-chain in the blends and thus evidenced the compatibility of two polymers on a molecular level. The IR spectra, DSC also explored the interaction changing during the temperature increasing and indicated that a significant conformational change took place. Received: 1 June 1998/Revised version: 1 October 1998/Accepted: 13 October 1998     

Miscibility and morphology in blends of poly(l-lactic acid) and poly(vinyl acetate-co-vinyl alcohol)

Poly(vinyl acetate-co-vinyl alcohol) copolymers [P(VAc-co-VA)] were prepared by acidic hydrolysis of poly(vinyl acetate) (PVAc) at various reaction time, and the degree of hydrolysis was analyzed by ¹³C nuclear magnetic resonance spectroscopy (NMR). Blends of poly(l-lactic acid) (PLA) and P(VAc-co-VA) were prepared by a solvent casting method using chloroform as a co-solvent. The PLA/PVAc blends exhibited a single glass transition over the entire composition range, indicating that the blends were miscible systems. On the contrary, for the blends with even 10% hydrolyzed PVAc copolymer, the phase separation and double glass transition were observed. With increasing neat PVAc contents, the heat of fusion decreased and the melting peaks shifted to lower temperature. The interaction parameter indicated negative values for up to 10% hydrolyzed samples, but positive values at more than 20% hydrolyzed one. Small angle X-ray scattering analysis revealed that the long period and the amorphous layer thickness increased with PVAc composition, suggesting that a considerable amount of PVAc component located in the interlamellar region. Polarized optical microscopy showed that the texture of spherulites became rougher on increasing the PVAc content. In the case of P(VAc-co-VA) copolymer, the intensity of polarized light decreased significantly, indicating that P(VAc-co-VA) component seemed to be expelled out of the interfibrillar regions. Scanning electron microscopy analysis revealed that the significant phase separation occurred with increasing the degree of hydrolysis. In the case of 70/30 blend of PLA and P(VAc-co-VA) with 30 mol% vinyl alcohol, the P(VAc-co-VA) copolymer formed the regular domains with a size of about 10 μm.     

Miscibility and crystallization behavior of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/poly(vinyl acetate) blends

The miscibility and crystallization behavior of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (P(HB‐co‐HV))/poly(vinyl acetate) (PVAc) blends have been investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). It was found that P(HB‐co‐HV)/PVAc blends were miscible in the melt over the whole compositions. Thus the blend exhibited a single glass transition temperature (T_g), which increased with increasing PVAc composition. The spherulitic morphologies of P(HB‐co‐HV)/PVAc blends indicated that the PVAc was predominantly segregated into P(HB‐co‐HV) interlamellar or interfibrillar regions during P(HB‐co‐HV) crystallization because of the volume‐filled spherulites. As to the crystallization kinetics study, it was found that the overall crystallization and crystal growth rates decreased with the addition of PVAc. The kinetics retardation was primarily attributed to the reduction of chain mobility and dilution of P(HB‐co‐HV) upon mixing with higher T_g PVAc. The overall crystallization rate was predominantly governed by the spherulitic growth rate and promoted by the samples treated with the quenched state because of the higher nucleation density. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 980–988, 2006     

Fourier transform infrared spectroscopic studies of the poly(styrene-co-acrylonitrile) and poly (vinyl chloride-co-vinyl acetate) blends

The Fourier transform infrared (FTIR) spectroscopic studies of the poly-(styrene-co-acrylonitrile) (SAN) and poly(vinyl chloride-co-vinyl acetate) (VYHH) blends produced by different blending techniques, viz., solution blending, melt-blending, and also the co-precipitation methods of blending, were performed. In the case of miscible blend systems, substantial band shiftings took place, whereas immiscible blend systems showed slight or no band shifting. The miscible blends showed a substantial residual spectrum which was absent in the case of the immiscible system when a similar subtraction process was carried out. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 991–1000, 1997     

Synthesis and biological activities of copolymers of N-glycinyl maleimide with methacrylic acid and vinyl acetate

Copolymerizations of N-glycinylmaleimide (GMI) with methacrylic acid (MA) and vinyl acetate (VAc) were carried out in 2-butanone using lauroylperoxide as an initiator at 70°C. Synthesized GMI, poly(GMI-co-MA), and poly(GMI-co-VAc) were characterized by IR and ¹H-NMR spectroscopies, elemental analysis, and gel permeation chromatography. The in vitro cytotoxicities of poly(GMI-co-MA) and poly(GMI-co-VAc) were evaluated using K-562 human leukemia cells and HeLa cells. From the cytotoxicity data against HeLa cells, the copolymers are less cytotoxic than monomeric GMI at dosage of 0.02, 1.0, and 5.0 mg/mL. Copolymers were very effective at any dosage tested. The in vivo antitumor activities of poly(GMI-co-MA) and poly(GMI-co-VAc) were also evaluated against mice bearing sarcoma 180. Monomeric GMI and its copolymers showed higher antitumor activity than 5-fluorouracil (5-FU) at any dosage tested. © 1995 John Wiley & Sons, Inc.     

Rheological studies of the poly(styrene-co-acrylonitrile) and poly(vinyl chloride-co-vinyl acetate) blends

The rheological studies of the poly(vinyl chloride-co-vinyl acetate) and poly(styrene-co-vinyl acetate) and poly(styrene-co-acrylonitrile) blends were performed by a Brabender Rheotron at three different temperatures and also at different shear rates. Flow curves of the blends at different temperatures were drawn. The flow behavior index and, also, zero-shear viscosity of the blends at different temperatures were determined. From the flow curves, it has been found that as shear stress increases, melt viscosity decreases at all temperatures, indicating that pseudoplastic behavior and experimental values lies above the line of the log-additivity value and below the line of the additivity rule of mixture. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2577–2583, 1998     

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     

Study of miscibility of melamine-formaldehyde resin and poly(vinyl acetate) blends for use as adhesives in engineered flooring

The objective of this research was to investigate the miscibility behavior of melamine-formaldehyde (MF) resin and poly(vinyl acetate) (PVAc) blends for their use as adhesives for bonding fancy veneer and plywood in engineered flooring, by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FT-IR). Blends of various compositions of MF resin/PVAc were prepared. To determine and compare the effect of PVAc content, blends with PVAc to MF resin weight ratios of 0, 30, 50, 70 and 100% were prepared. These blends displayed a single cure temperature over the entire range of compositions indicating that this blend system was miscible in the amorphous phase due to the formation of hydrogen bonding between the amine groups of the MF resin and the carbonyl groups of PVAc.     

New miscible blends composed of polysulfone and poly(1-vinylpyrrolidone-co-acrylonitrile) copolymers and their phase behavior

The miscibility of polysulfone, PSf, blend with poly(1-vinylpyrrolidone), PVP, and that of PSf blend with poly(1-vinylpyrrolidone-co-acrylonitrile) copolymers, P(VP-AN), containing various amount of VP were explored. Even though PSf did not formed miscible blends with PVP when both components had high molecular weight, it formed miscible blend with PVP by decreasing molecular weight of PVP. PSf also formed homogeneous mixtures with P(VP-AN) containing AN from 2 to 16 wt%. These miscible blends underwent phase separation on heating caused by LCST-type (lower critical solution temperature-type) phase behavior. The phase separation temperature of miscible blends first increases with AN content, goes through a maximum centered at about 8 wt% AN. Interaction energies of binary pairs involved in blends were evaluated from the observed phase boundaries using the lattice-fluid theory. The decline of the contact angle between water and blend film by increasing P(VP-AN) content in blend indicated that the hydrophobic properties of PSf could be improved by blending with P(VP-AN) copolymers.     

Selective hydrogen bonding and hierarchical nanostructures in poly(hydroxyether of bisphenol A)/poly(?-caprolactone)-block-poly(2-vinyl pyridine) blends

The phase behavior, hydrogen bonding interactions and morphology of poly(hydroxyether of bisphenol A) (phenoxy) and poly(?-caprolactone)-block-poly(2-vinyl pyridine) (PCL-b-P2VP) were investigated using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, optical microscopy and atomic force microscopy (AFM). In this A-b-B/C type block copolymer/homopolymer system, both P2VP and PCL blocks have favorable intermolecular interaction towards phenoxy via hydrogen bonding. However, the hydrogen bonding between P2VP and phenoxy is significantly stronger than that between PCL and phenoxy. Selective hydrogen bonding between phenoxy/P2VP pair at lower phenoxy contents and co-existence of two competitive hydrogen bonding interactions between phenoxy/P2VP and phenoxy/PCL pairs at higher phenoxy contents were observed in the blends. This leads to the formation of a variety of composition dependent nanostructures including wormlike, hierarchical and core-shell morphologies. The blends became homogeneous at 95 wt% phenoxy where both blocks of the PCL-b-P2VP were miscible with phenoxy due to hydrogen bonding. In the end, a model was proposed to explain the microphase morphology of blends based on the experimental results obtained. The swelling of the PCL-b-P2VP block copolymer by phenoxy due to selective hydrogen bonding causes formation of different microphases.     

Thermal,Spectroscopic, and Mechanical Properties of Blend Films of Poly(N-Vinyl-2-Pyrrolidone) and Sodium Alginate

Blends of poly(N-vinyl-2-pyrrolidone) (PVP) and sodium alginate (NaAlg) were prepared by casting from aqueous solutions. These blends were characterized by Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and tensile strength test. The miscibility in the blends of PVP and NaAlg was established on the basis of the thermal analysis results. DSC showed that the blends possessed single, composition-dependent glass transition temperatures (T _g s), indicating that the blends are miscible in amorphous state. FT-IR studies indicate that there are the intermolecular hydrogen bonding interactions, i.e., –OH·····O=C in PVP/NaAlg blends. This blend films also exhibited the higher thermal stability and improved the elongation at break in dry states.     

Miscibility studies of polymer blends by viscometry methods

The intrinsic viscosities of blends of poly(vinyl chloride)/poly(ethylene-co-vinyl acetate) (PVC/EVA), poly(vinyl chloride)/poly(styrene-co-acrylonitrile) (PVC/SAN), and poly(ethylene-co-vinyl acetate)/poly(styrene-co-acrylonitrile) (EVA/SAN) have been studied in cyclohexanone as a function of blend composition. In order to predict the compatibility of polymer pairs in solution, the interaction parameter term, Δb, obtained from the modified Krigbaum and Wall theory, and the difference in the intrinsic viscosities of the polymer mixtures and the weight average intrinsic viscosities of the two polymer solutions taken separately are used. © 1994 John Wiley & Sons, Inc.     

Processability enhancement of poly(lactic acid-co-ethylene terephthalate) by blending with poly(ethylene-co-vinyl acetate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and poly(butylene succinate)

Processability enhancement feasibility of an in-house synthesized poly(lactic acid-co-ethylene terephthalate), PLET, is investigated by blending with commercial poly(ethylene-co-vinyl acetate), EVA, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), PHBV, and poly(butylene succinate), PBS. The three blend systems are prepared by varying PLET contents, and their properties are characterized. DSC, SEM, and FTIR results indicate that PLET/EVA blends are immiscible, while the corresponding PLET/PBS and PLET/PHBV blends are miscible and partially miscible, respectively. DMA results show that the three blend systems have storage modulus comparable to those of commercial EVA, PHBV, and PBS, when PLET content is kept lower than 50, 25, and 25 wt%, respectively. PLET/EVA blends show higher thermal stability, compared to those of the other two blend systems. Results on degradability tests indicate that PLET/PBS blends show highest hydrolytic degradability, compared to the other two blends, as both blend constituents are associated in the hydrolytic degradation.     

Miscibility and intermolecular hydrogen‐bonding interactions in poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)/poly(4‐vinyl phenol) binary blends

The miscibility and hydrogen bonding interaction in the poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)/poly(4‐vinyl phenol) [P(3HB‐co‐3HH)/PVPh] binary blends were investigated by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The DSC results indicate that P(3HB‐co‐3HH) with 20 mol % 3HH unit content is fully miscible with PVPh, and FTIR studies reveal the existence of hydrogen bonding interaction between the carbonyl groups of P(3HB‐co‐3HH) and the hydroxyl groups of PVPh. The effect of blending of PVPh on the mechanical properties of P(3HB‐co‐3HH) were studied by tensile testing. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007