Representation of vapor–liquid and liquid–liquid equilibria for binary systems containing polymers: Applicability of an extended flory–huggins equation

For some binary systems, an extended Flory–Huggins equation is applicable to both vaporliquid equilibria (VLE) and liquid–liquid equilibria (LLE) using the same adjustable parameters. New LLE and VLE data are reported for polystyrene (PS) (MW = 100,000)/cyclohexane and for poly(ethylene glycol) (PEG) (MW = 8,000)/water. Experimental results for the PS/cyclohexane system agree well with the semiempirical model, whereas those for PEG/water do not, probably because, for PEG/water, the temperature range of the VLE data is about 55°C lower than that of the LLE data. Excellent fits were obtained for our previously published experimental results for PS/cyclohexane (upper critical solution temperature, UCST), PS/ethyl acetate (lower critical solution temperature, LCST), PS/tert-butyl acetate and PS/methyl acetate (both UCST and LCST), and PEG/water (closed-loop). The semiempirical model also fits well with new data obtained for the polymer blend PS/poly(vinyl methyl ether). © 1993 John Wiley & Sons, Inc.     

Recycling of high density polyethylene/poly(vinyl chloride)/polystyrene ternary mixture with the aid of high energy radiation and compatibilizers

Ternary mixtures of waste plastics of high density polyethylene (HDPE), poly(vinyl chloride) (PVC), and polystyrene (PS) was recycled using a single‐screw extruder. Poly(ethylene‐co‐vinyl acetate) and poly(styrene‐b‐ethylene/butylenes‐b‐styrene) were introduced as compatibilizers for HDPE/PVC and HDPE/PS, respectively. After the polymer blends was prepared via extrusion, they were subjected to high energy irradiation. The morphology and the mechanical properties of the hybrid blends were examined. Scanning electron micrographs and transmission electron micrographs showed that both compatibilizers and irradiation improved the uniformity and dispersion of the system. The heterogeneous crosslinking generated by irradiation resulted in an optimum impact strength. High elongation at break was achieved by using compatibilizers. The improvement of tensile strength was moderate. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 12: 2756–2762, 2003     

Surface modification of LDPE with PE‐PEO graft copolymer

Films of LDPE containing 1–10 wt % of various polymeric additives were prepared by different techniques. Three poly(ethylene‐graft‐ethylene oxide)s synthesized by grafting poly(ethylene‐co‐acrylic acid) with poly(ethylene oxide) monomethyl ether (MPEO), and two pure MPEOs having molecular weights 750 and 2000 were used as additives. The additives were mixed with LDPE both by blending in a common solvent and by melt mixing. The blends were then solvent cast from xylene onto glass Petri dishes or compression molded between glass plates. The film surfaces were studied by water contact angle measurements and by X‐ray photoelectron spectroscopy (XPS), and melting points and heats of melting were recorded by differential scanning calorimetry (DSC). The blends had a two‐phase morphology, with enrichment of the graft copolymers at the glass–polymer interface, as shown by contact angle values and XPS spectra. Large differences in the interface accumulation between the different film samples were observed. Films prepared by compression molding of solution‐mixed blends exhibited much lower surface accumulation of graft copolymer at the glass–polymer interface than did the solvent cast or melt‐mixed/compression‐molded samples. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 316–326, 2000     

Flame retardancy of some ethylene–vinyl acetate copolymer‐based formulations

The combustion behaviour and thermal decomposition of ethylene–vinyl acetate copolymer (EVA) (26 wt% vinyl acetate content) formulations containing alumina trihydrate, ammonium polyphosphate, melamine, pentaerythritol and their co‐mixtures, were studied using cone calorimetry and thermogravimetric analysis. Formulations containing ammonium polyphosphate burned with the formation of intumescent carbonaceous chars, with EVA acting as a carbonization agent. EVA materials containing ammonium polyphosphate (20 wt%), with a sufficient amount of alumina trihydrate or melamine, were superior to the non‐intumescent alumina trihydrate and melamine containing formulations in terms of the heat release rate, mass loss rate and smoke production. Melamine showed some smoke suppressant effect and significant CO reducing properties. However, the melamine–EVA and melamine–alumina trihydrate–EVA showed a very high heat release rate. Thermogravimetric studies showed that oxygen played a favourable role in enhancing the char formation by encouraging active participation of the polymer matrix in the interaction with polyphosphoric acid. Copyright © 2000 John Wiley & Sons Ltd.     

Synthesis and properties of styrene–EPDM–vinyl acetate graft polymer

The styrene–EPDM–vinylacetate (SEV) graft polymer, which linked respectively the styrene (St) unit and vinylacetate the (VAc) unit to the ethylene–propylene–diene terpolymer (EPDM) backbone was synthesized by two‐step graft polymerizations: First the graft polymerization of VAc onto EPDM was carried out, and then St was added successively in the prepolymerized solution and further polymerized for a given period to obtain SEV. The effects of concentration of EPDM and an initiator, mole ratio of VAc to St, polymerization time, temperature, and solvent were examined on the graft polymerizations. The synthesized graft polymers (SEVs) that have different contents of St or VAc were identified by Fourier transform IR spectrum. The highest graft ratio has been obtained by 10 wt % of EPDM, 1.0 mole ratio of VAc to St, and 1.0 wt % of BPO in toluene for 48 h at 70°C. The glass transition temperature of SEV is lower than that of poly(vinyl acetate) (PVAc) and polystyrene (PS). The thermal stability of SEV is higher than that of PVAc, PS, and the acrylonitrile–butadiene–styrene (ABS) resin. The tensile strength of SEV was improved as compared with that of EPDM. The light resistance and weatherability of SEV were better than those of ABS. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2296–2304, 2000     

A theoretical and experimental heat of mixing study for polymer‐polymer mixtures

Heat of mixing is introduced as a guide for phase stability predictions of polymer mixtures, and an appropriate equation is presented for it. The form of this equation is a combined function of temperature and mixture composition. The capability of the presented equation has been treated qualitatively and it has been shown that all types of exothermic, endothermic, and s‐shaped or sigmoidal heat of mixing curves can be produced. Utilizing the low molecular weight analogue calorimetry method, heat of mixing was measured at two temperatures, 27°C and 37°C for three polymer mixtures—poly(styrene)/poly(vinylchloride) (PS/PVC), poly(styrene)/ poly(methylmethacrylate) (PS/PMMA), and poly(styrene)/poly(vinylacetate) (PS/ PVAc) at an entire composition range. It has been shown that excellent agreement between the results of the calculations and the experimental heat of mixing data was achieved. Using the results of analogue calorimetric measurements for phase stability studies of polymer mixtures, it was found that often, acceptable predictions can be made by this method, but they are not always completely true.     

Cocontinuous morphologies in polystyrene/ethylene–vinyl acetate blends: The influence of the processing temperature

The influence of the compression‐molding temperature on the range of cocontinuity in polystyrene (PS)/ethylene–vinyl acetate (EVA) copolymer blends was studied. The blends presented a broad range of cocontinuity when compression‐molded at 160°C, and they became narrower when compression‐molded at higher temperatures. A coarsening effect was observed in PS/EVA (60:40 vol %) blends upon compression molding at higher temperature with an increase in the phase size of the cocontinuous structure. Concerning PS/EVA (40:60 vol %) blends, an increase in the mixing and molding temperatures resulted in a change from a cocontinuous morphology to a droplet–matrix morphology. This effect was observed by selective extraction experiments and scanning electron microscopy. The changes in the morphology with the molding conditions affected the storage modulus. An increase in the storage modulus in blends compression‐molded at 160°C was observed as a result of dual‐phase continuity. An EVA copolymer with a higher vinyl acetate content (28 wt %) and a higher melt‐flow index resulted in blends with a broader range of cocontinuity. This effect was more pronounced in blends with lower amounts of PS, that is, when EVA formed the matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 386–398, 2003     

Dynamic–mechanical properties of modified poly(ethylene‐co‐vinyl acetate)

To study the relationship among relaxation peaks observed in dynamic mechanical experiments and the structure of poly(ethylene‐co‐vinyl acetate) (EVA), EVA copolymers with different substitution in the carbonyl group were synthesized. EVA was hydrolyzed to obtain poly (ethylene‐co‐vinyl alcohol) and was subsequently reacted with formic, hexanoic, and octanoic acids. The copolymers synthesized were characterized by infrared spectroscopy. Analysis of the DMA spectra of the copolymers showed that their relaxation behavior depends on the vinyl acetate concentration. The α‐ and β‐transitions were observed in EVA copolymers with 8 and 18 wt % of functional groups, and the relationship among relaxation process with the structure of polymer was investigated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1371–1376, 2005     

Effect of styrene‐butadiene‐styrene addition on polystyrene/high‐density polyethylene blends

In order to prepare an ideal mixture, the physical and chemical properties of the constituent polymers must be known in detail. Thus, selection of the polymers that will constitute the mixture and a thorough study of the mixing methods and the economic factors become important. A rigid plastic is toughened by dispersing a small amount of rubbery material (generally 5–20%) in the rigid plastic matrix. Such a mixture of plastics is characterized by its impact resistance. Among thermoplastics toughened in this way are polystyrene (PS), poly(vinyl chloride), poly(methyl methacrylate), polypropylene, polycarbonate, and nylons, and recently thermoset resins such as epoxies, unsaturated polyester resins, and polyamids. In this study PS and high‐density polyethylene polymers were mixed in various ratios. In order to increase the compatibility of the mixtures, 5, 7.5, and 10% SBS copolymer was also added. The mixing operation was conducted by using a twin‐screw extruder. The morphology and the compatibility of the mixtures were examined by using SEM and DSC techniques. Furthermore, the elastic modulus, yield and tensile strengths, percent elongation, Izod impact resistance, hardness, and melt flow index values of the polymer alloys of various ratios were determined. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2967–2975, 2002; DOI 10.1002/app.2325     

Preparation and characterization of binary blends composed of poly(dioctylfluorene‐alt‐hexylsulfonylthiophene) and nonconjugated polymers

The solutions and the thin films of poly[9,9‐dioctyl‐2,7‐fluorene‐alt‐2,5–(3‐hexyl‐sulfonylthiophene)] (PFSO₂T) and its binary blends with other nonconjugated polymers such as poly(methyl methacrylate) (PMMA), polycarbonate (PC), and ethylene vinyl acetate copolymer (EVA) can be prepared by different concentrations from a polymer solution. Binary polymer blends can increase the absorbance and photoluminescence intensities in the solid state due to nonconjugated polymers can act as dispersion agents which can reduce the interchain interaction or the aggregation of the conjugated polymers. Photoluminescence intensity of the thin films of fluorescent polymers blending with ethylene vinyl acetate copolymers exhibited six times higher than that of the neat fluorescent polymers. The PFSO₂T/EVA binary blends reveal the least extent of optical degradation of around 20% compared to those binary blends in both absorption and emission intensities after the irradiation under the UV‐light for 20 h. The cross‐sectional morphology of fluorescent polymers blending with ethylene vinyl acetate copolymers reveals little aggregation and better phase separation among the other binary polymer blends. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44969.     

Further evidence for the effects of critical concentration fluctuations on the diffusion-controlled reaction kinetics in binary polymer mixtures

Summary Kinetics of the intramolecular photodimerization reaction of a molecular probe, 9-(hydroxymethyl)-10-[(Naphthylmethoxy)-methyl] anthracene (HNMA) was studied in the miscible region of binary polymer mixtures. Poly(ethylene oxide)/poly(methyl methacrylate)(PEO/PMMA), polystyrene/poly(vinyl methyl ether) (PSH/PVME) and deuterated polystyrene/poly(vinyl methyl ether) (PSD/PVME) mixtures were used as binary polymer blends. It was found that the reaction kinetics is strongly affected by the concentration fluctuations in the vicinity of the coexistence curve. These behavior are consistent with the magnitude of the binary interaction parameters X estimated from the small-angle neutron-scattering and the melting point depression data. These experimental results confirm the fact that the reaction kinetics of HNMA reflects the concentration fluctuations with the wavelength comparable to the dimension of the probe.     

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.     

Thermodynamic interactions of EVA copolymer‐solvent systems by inverse gas chromatography measurements

The solubility parameter and the Flory–Huggins interaction parameter of two EVA (ethylene–vinyl acetate) copolymers, each one with different vinyl acetate content, are calculated by using inverse gas chromatography technique. The influence of the vinyl acetate percentage is analyzed and indicates that the polymer–solvent interactions are stronger in the case of the copolymer with the highest vinyl acetate percentage. The results also point to the fact that the most favorable solvents for the studied materials are the aromatic‐type ones. Finally, from the calculated values of the polymer solubility parameter (16.3 MPa^0.5 for EVA 460 and 15.1 MPa^0.5 for EVA410, at 50°C), it can be noticed that the solubility parameter of the EVA copolymer with the largest vinyl acetate content is the closest to the solubility parameter of pure vinyl acetate. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Comparison of interdiffusion at polystyrene–poly(vinyl methyl ether) and polystyrene–poly(isobutyl vinyl ether) interfaces

The effect of polymer–polymer compatibility on interdiffusion at polymer interfaces with dissimilar mobilities was investigated by attenuated total internal reflectance infrared spectroscopy. The polymer pair consisting of polystyrene and poly(vinyl methyl ether) was used to study interdiffusion at the interface of compatible polymers. The polymer pair consisting of polystyrene and poly(isobutyl vinyl ether) was used to study interdiffusion at the interface of incompatible polymers. Results indicate that the extent of interdiffusion is controlled by the polymer–polymer compatibility parameter, irrespectively of the differences in the mobility of the polymers.     

Preparation of well‐controlled porous carbon nanofiber materials by varying the compatibility of polymer blends

The relationships between the compatibility in binary polymer blends and the pore sizes of carbon nanofibers (CNFs) prepared from the blends were investigated. Compatibility was determined by the difference between the solubility parameters of each polymer in the polymer blends. Porous CNFs were prepared by an electrospinning and carbonization process using binary polymer blends, consisting of polyacrylonitrile (PAN) as the carbonizing polymer and poly(acrylic acid) (PAA), poly(ethylene glycol), poly(methyl methacrylate) or polystyrene (PS) as the pyrolyzing polymer. The pore size of the CNFs increased with increasing difference in solubility parameter. The CNFs prepared using the PAN/PAA blend, which had the smallest solubility parameter difference, exhibited a pore size of 1.66 nm compared to 18.24 nm for the CNFs prepared using the PAN/PS blend. The prepared CNF webs with controlled meso‐sized pores showed a stable cycle performance in cyclic voltammetry measurements and improved impedance characteristics. This method focusing on the compatibility in polymer blends was simple to apply and effective for controlling the pore sizes and surface area of CNFs for application as electrode materials in energy storage systems. © 2013 Society of Chemical Industry     

High‐resolution solid‐state NMR and SEM study of the interaction behavior of poly(ethylene‐co‐vinyl acetate)/poly(vinyl acetate) blends

Binary blends formed by two types of ethylene‐co‐vinyl acetate (EVA), which have different vinyl acetate contents, and poly(vinyl acetate) (PVAc) were prepared in a Haake Rheocord 9000 plastograph. A series of samples were obtained varying the PVAc amount up to 50%. The studies were carried out employing solid‐state nuclear magnetic resonance spectroscopy (NMR) and scanning electronic microscopy (SEM). The xenon‐129 (¹²⁹Xe) and carbon‐13 (¹³C) NMR response together with the microscopy results showed that the systems are heterogeneous. Therefore, EVA with a higher vinyl acetate content presented some interaction between the polymer blend components. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 116–124, 2002     

Synthesis of poly(vinyl acetate)‐graft‐polystyrene and application to preparation of porous membranes

Poly(vinyl acetate)–TEMPO (PVAc–TEMPO) macroinitiators were synthesized by bulk polymerization of vinyl acetate in the presence of benzoyl peroxide (BPO) followed by termination with 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO). Radicals were mainly transferred to the acetoxy methyl groups in PVAc during the polymerization. The PVAc–TEMPO macroinitiators had several TEMPO‐dormant sites and styrene bulk polymerization with the macroinitiators produced poly(vinyl acetate)‐graft‐polystyrene (PVAc‐g‐PS). All the TEMPO‐dormant sites of PVAc–TEMPO macroinitiators participated in the styrene polymerization with almost equal reactivity. Methanolysis of PVAc‐g‐PS broke the PS branches apart from the PVAc backbone chains. Hydrophobic or hydrophilic porous membranes with controlled pore size could be prepared by removing the PVAc domains or the PS domains from the graft copolymer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1658–1667, 2001     

Solid‐state NMR and morphological studies of poly(ethylene‐co‐vinyl acetate)/poly(vinyl acetate) blends

To obtain a correlation among structure–morphology–mobility–compatibility properties of poly(ethylene‐co‐vinyl acetate) (EVA)/poly(vinyl acetate) (PVAc) blends, we have used scanning electron microscopy and solid‐state nuclear magnetic resonance in our investigations. The results are discussed in terms of blends, component dispersion, plasticization effect, and domain mobilities to acquire a response of the correlation between structural properties. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2990–2996, 1999     

Anomalous mechanical behavior upon recycling of poly(phenylene‐ether)‐based thermoplastic elastomer

Recycling of thermoplastic elastomers based on poly (phenylene ether) (PPE) was studied in detail. The quaternary blend comprising of styrene–ethylene–butylene–styrene (SEBS)/ethylene vinyl acetate (EVA)/PPE‐PS (polystyrene) showed improvement in mechanical properties upon recycling, which was correlated with the formation of crosslinked network in the system. Presence of crosslinked network was confirmed by the gel content analysis. The blend components involved in the crosslinking were evaluated by gel morphology analysis. Fourier transform infrared spectroscopy revealed the chemical composition of the crosslinked gel. Crosslinking mechanism was established based on the reactivity of allylic EVA radical during recycling. Rheological study supported the notion of crosslinking upon recycling that resulted in higher storage modulus (G′) as a manifestation of restrained flow by network formation. On the basis of the earlier data, a reaction mechanism for crosslinking was proposed. Finally, structure–property correlation was developed through morphological, chemical, and rheological analysis to understand the anomalous enhancement in mechanical properties upon recycling. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Preparation of core–shell poly(acrylic acid)/polystyrene/SiO2 hybrid microspheres

Core–shell poly(acrylic acid)/polystyrene/SiO₂ (PAA/PS/SiO₂) hybrid microspheres were prepared by dispersion polymerization with three stages in ethanol and ethyl acetate mixture medium. Using vinyltriethoxysilane (VTEOS) as silane agent, functional silica particles structured vinyl groups on surfaces were prepared by hydrolysis and polycondensation of tetraethoxysilane and VTEOS in core stage. Then, the silica particles were used as seeds to copolymerize with styrene and acrylic acid sequentially in shell stage I and stage II to form PAA/PS/SiO₂ hybrid microspheres. Transmission electron microscope results show that most PAA/PS/SiO₂ hybrid microspheres are about 40 nm in diameter, and the silica cores are about 15 nm in diameter, which covered with a layer of PS about 7.5‐nm thick and a layer of PAA about 5‐nm thick. This core–shell structure is also conformed by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and differential scanning calorimetry. FTIR results show that silica core, PS shell, and PAA outermost shell are bonded by covalents. In the core–shell PAA/PS/SiO₂ hybrid microsphere, the silica core is rigidity, and the PAA outermost shell is polarity, while the PS layer may work as lubricant owning to its superior processing rheological property in polymer blending. These core–shell PAA/PS/SiO₂ hybrid microspheres have potential as new materials for polar polymer modification. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1729–1733, 2006