Synthesis and antitumor activity of poly(3,4‐dihydro‐2H‐pyran‐co‐maleic anhydride‐co‐vinyl acetate)

The radical‐initiated terpolymerization of 3,4‐dihydro‐2H‐pyran (DHP), maleic anhydride (MA), and vinyl acetate (VA), which were used as a donor–acceptor–donor system, was carried out in methyl ethyl ketone in the presence of 2,2′‐azobisisobutyronitrile as an initiator at 65°C in a nitrogen atmosphere. The synthesis and characterization of binary and ternary copolymers, some kinetic parameters of terpolymerization, the terpolymer‐composition/thermal‐behavior relationship, and the antitumor activity of the synthesized polymers were examined. The polymerization of the DHP–MA–VA monomer system predominantly proceeded by the alternating terpolymerization mechanism. The in vitro cytotoxicities of poly(3,4‐dihydro‐2H‐pyran‐alt‐maleic anhydride) [poly(DHP‐alt‐MA)] and poly(3,4‐dihydro‐2H‐pyran‐co‐maleic anhydride‐co‐vinyl acetate) [poly(DHP‐co‐MA‐co‐VA)] were evaluated with Raji cells (human Burkitt lymphoma cell line). The antitumor activity of the prepared anion‐active poly(DHP‐alt‐MA) and poly(DHP‐co‐MA‐co‐VA) polymers were studied with methyl–thiazol–tetrazolium testing, and the 50% cytotoxic dose was calculated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2352–2359, 2005     

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     

Evaluation of mechanical properties and physical interactions of a ternary blend of poly(ethylene‐co‐octene)/poly(ethylene‐co‐vinyl acetate)/poly(vinyl chloride) in the molten state

In this work, ethylene‐co‐vinyl acetate (EVA), poly(ethylene‐co‐octene) (POE), and poly(vinyl chloride) (PVC) blends were processed in a molten state process using a corotating twin‐screw extruder to assess both the balance of mechanical properties and physical interactions in the melt state. Tensile measurements, scanning electron microscopy, and oscillatory rheometry were performed. By means of flow curves, the parameters of the power law as well as the distribution of relaxation times were assessed with the aid of a nonlinear regularization method. The mechanical properties for the EVA‐POE blend approximated the values for POE, while inclusion of PVC shifted the modulus values to those of neat EVA. The rise in modulus was corroborated by the PVC phase dispersion as solid particles that act as a reinforcement for the ternary blend. The rheological properties in the molten state show that the POE does not present molecular entanglement effects and so tends both to diminish the EVA mechanical properties and increase the fluidity of the blend. However, the addition of PVC both restored the EVA typical pseudoplastic feature and promoted the increase in the viscosity and the mechanical properties of the ternary blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Study on segmental interaction parameter between ethylene and vinyl acetate monomer units of EVA by inverse gas chromatography

A method of analysis of inverse gas chromatography (IGC) measurements on copolymers to calculate segmental interaction parameters was proposed. Poly(ethylene‐co‐vinyl acetate) (EVA), poly(vinyl acetate) (PVAc), and dotriacontane (C32) were studied at 120°C with eight different probes of varying polarities by IGC. The value of the segmental interaction parameter between ethylene units and vinyl acetate units in EVA was found to be 1.18, which is consistent with the literature values. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 693–698, 1999     

Optimization of engineering and solvent resistive behavior of high vinyl acetate content EVA‐modified poly(ethylene‐co‐1‐octene) interpenetrating network blends using taguchi orthogonal array

Process parameters of poly (ethylene‐co‐vinyl acetate) (EVA)‐modified poly (ethylene‐co‐1‐octene) (POE)‐interpenetrating, double network blend was designed through Taguchi L9 orthogonal array as a novel approach for complete optimization of engineering and solvent‐swelling properties. Influence of different factors like EVA and peroxide concentrations, blending temperature, and blending time on gel content, tensile modulus, tensile strength, ultimate elongation were statistically calculated. Results showed good correlation between mathematical and physical inferences. Stress relaxation, hysteresis and other physico‐mechanicals like total elongation, solvent‐swelling, etc., were interestingly depended upon the nature of dominantly crosslinked phase instead of net crosslinking of the network hybrids. Sorption, on the other hand, depended on the hydrophobic‐hydrophilic property of the surfaces. The series of data produced finally helped to select the best process parameters under which a particular POE‐EVA blend composition yielded most balanced physico‐mechanicals. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

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     

Preparation and properties of microcapsule with EVA core‐PU shell structure

Microcapsule with poly(ethylene‐co‐vinylacetate) (EVA) core‐polyurethane (PU) shell structure was synthesized by interfacial polymerization in aqueous polyol dispersion with ethylene diamine as the chain extender of toluene diisocyanate in poly(vinyl alcohol) aqueous solution as the stabilizing agent. The effects of polyol constituent on the average particle size and distributions, morphologies, color strength, and friction fastness of core‐shell particles were investigated to design microcapsule. The friction fastness of printed fabrics with EVA core‐PU shell microcapsules became the increase to 4–5 grades. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 893–902, 2007     

Synthesis and properties of polymeric biocides based on poly(ethylene‐co‐vinyl alcohol)

Poly(ethylene‐co‐vinyl acetate) with 55 wt % vinyl acetate units (EVA55) was cryogenically ground and saponified in KOH/ethanol solution to obtain poly(ethylene‐co‐vinyl alcohol) (EVOH55). Polymeric antimicrobial agents were synthesized by reacting three antimicrobial agents, 4‐aminobenzoic acid (ABA), salicylic acid (SA), and 4‐hydroxy benzoic acid (HBA) with EVOH55. The polymers became more flexible and exhibited lower melting peak temperature and heat of fusion as the content of the chemically bound ABA, SA, and HBA units increased. These phenomena appeared more significant in the order of ABA < HBA < SA. S. aureus, Gram‐positive bacterium, was more susceptible to the polymeric antimicrobial agents than P. aeruginesa, Gram‐positive bacterium. The antimicrobial activity increased in the order of EVOH55‐HBA < EVOH55‐ABA < EVOH‐SA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 765–770, 2004     

Acrylate/EVA reactive blends and semi‐IPN: Chemical,chemical–physical,and thermo‐optical characterization

In the present work, blends between poly(methyl methacrylate) (PMMA) or its copolymer with butyl methacrylate P(MMA‐co‐BMA) and poly(ethylene‐co‐vinyl acetate) (EVA) rubbers obtained applying the reactive blending principles were deeply investigated to clarify the chemistry of the system. A copolymeric phase, which is created in situ, was isolated and its chemical structure was determined through NMR analysis. The blends were also crosslinked with a flexible dimethacrylate to realize semi‐interpenetrated networks. The blends were characterized for their properties of interest (mechanical and optical behaviors). Particularly, an accurate investigation of the optical properties as a function of the temperature was performed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synthesis of block copolymers via redox polymerization

Polymerization and copolymerization of vinyl monomers such as acrylamide, acrylonitrile, vinyl acetate, and acrylic acid with a redox system of Ce(IV) and organic reducing agents containing hydroxy groups were studied. The reducing compounds were poly(ethylene glycol)s, halogen‐containing polyols, and depolymerization products of poly(ethylene terephthalate). Copolymers of poly(ethylene glycol)s‐b‐polyacrylonitrile, poly(ethylene glycol)s‐b‐poly(acrylonitrile‐co‐vinyl acetate), poly(ethylene glycol)s‐b‐polyacrylamide, poly(ethylene glycol)s‐b‐poly(acrylamide‐co‐vinyl acetate), poly(1‐chloromethyl ethylene glycol)‐bpoly(acrylonitrile‐co‐vinyl acetate), and bis[poly(ethylene glycol terephthalate)]‐b‐poly(acrylonitrile‐co‐vinyl acetate) were produced. The yield of acrylamide polymerization and the molecular weight of the copolymer increased considerably if about 4% vinyl acetate was added into the acrylamide monomer. However, the molecular weight of the copolymer was decreased when 4% vinyl acetate was added into the acrylonitrile monomer. Physical properties such as solubility, water absorption, resistance to UV light, and viscosities of the copolymers were studied and their possible uses are discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1385–1395, 1999     

Organic vapor permeation through natural rubber/poly(ethylene‐co‐vinyl acetate) blend membranes

Natural rubber/poly(ethylene‐co‐vinyl acetate) (NR/EVA) blend membranes, crosslinked with dicumyl peroxide, have been prepared and tested for vapor permeation characteristics. The effects of structure and morphology of the blend membranes on the permeability were investigated. The permeability was found to decrease with increase in EVA content which has been attributed to the semicrystalline nature of EVA. The permeation process has been observed to be controlled mainly by the molecular mass of the penetrants. In the case of benzene/acetone mixtures, it has been found that when acetone concentration increases the vapor permeation rate decreases. This clearly indicates less interaction of acetone towards NR/EVA membranes. For supporting all the observations, the parameters such as swelling coefficient and permeability coefficient have been calculated. POLYM. ENG. SCI., 48:198–202, 2008.© 2007 Society of Plastics Engineers     

Toughening and compatibilization of polypropylene/polyamide‐6 blends with a maleated–grafted ethylene‐co‐vinyl acetate

In this article, maleated–grafted ethylene‐co‐vinyl acetate (EVA‐g‐MA) was used as the interfacial modifier for polypropylene/polyamide‐6 (PP/PA6) blends, and effects of its concentration on the mechanical properties and the morphology of blends were investigated. It was found that the addition of EVA‐g‐MA improved the compatibility between PP and PA6 and resulted in a finer dispersion of dispersed PA6 phase. In comparison with uncompatibilized PP/PA6 blend, a significant reduction in the size of dispersed PA6 domain was observed. Toluene‐etched micrographs confirmed the formation of interfacial copolymers. Mechanical measurement revealed that the addition of EVA‐g‐MA markedly improved the impact toughness of PP/PA6 blend. Fractograph micrographs revealed that matrix shear yielding began to occur when EVA‐g‐MA concentration was increased upto 18 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99:3300–3307, 2006     

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 the molecular architecture of graft copolymers on the phase morphology and tensile properties of PS/EVA blends

Graft copolymers of poly(ethylene‐co‐vinyl acetate) (EVA) grafted with polystyrene (PS) with different molecular weight and different EVA/PS ratio were prepared by coupling reaction between acyl chloride functionalized PS (PS‐COCl) and hydrolyzed EVA. PS‐COCl with controlled molecular weight was prepared by anionic polymerization of styrene, followed by end capping with phosgene. The effect of the molecular architecture of the graft copolymer on the compatibilization of PS/EVA blends was investigated. Substantial improvement in the elongation at break and ductility was observed using the graft copolymer with PS segments with molecular weight as high as 66,000 g/mol and with a PS proportion equal or higher than EVA. The effect of the compatibilization on the morphology was also investigated by scanning electron microscopy and atomic force microscopy. The blend that presented the highest value of elongation at break also displayed dispersed phase constituted by inclusions of the PS phase inside the EVA particle forming a cocontinuous structure, as observed by AFM. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Production of polymeric membranes made of polypropylene,poly(ethylene‐co‐vinyl acetate), and poly(vinyl alcohol)

In this study, we prepared and characterized membranes containing polypropylene, poly(ethylene‐co‐vinyl acetate) (EVA), and poly(vinyl alcohol) (PVA). The production process involved blend extrusion and calendering followed by solvent extraction by toluene and water of the EVA and PVA phases. Morphology studies involving scanning electron microscopy determined the pore size distribution at the surface and in the internal regions of the membrane. The resulting membrane properties were related to the processing variables (extension rate, process temperature, and solvent extraction methods) and blend composition. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3275–3286, 2004     

Morphology,Resistivity, and PTC behavior of EVOH/CB composites prepared by solvent‐casting saponification and precipitation saponification

Poly(ethylene‐co‐vinyl alcohol)/carbon black (EVOH/CB) composites were prepared by a solvent‐casting saponification (‐D) and precipitation saponification (‐P) methods with a poly(ethylene‐co‐vinyl acetate)/CB (EVA/CB) toluene suspension. The effects of the CB content and saponification time on the morphology, electrical resistivity, thermal, and mechanical properties of EVA/CB composites were examined. The volume resistivity (ρ _v) of the EVA/CB‐D and EVA/CB‐P samples decreased significantly with increasing CB content and the percolation threshold of such composites was determined about 10 wt%. At 10 wt% of CB content, the ρ _v of EVA/CB‐D composite decreased significantly with the saponification time, whereas ρ _v of EVA/CB‐P composites did not change. As the saponification time increased, EVA/CB25wt% composites form cavity structure which CB is usually located in oval cavities larger than the particles themselves. This oval cavity structure almost resembles extruded high‐density polyethylene (HDPE)/CB composites. The morphology and PTC behavior of prepared composites were compared with those of HDPE/CB and the mechanism of PTC and NTC effects was discussed. POLYM. COMPOS., 38:1462–1473, 2017. © 2015 Society of Plastics Engineers     

Effects of poly(vinyl acetate) and poly(vinyl chloride‐co‐vinyl acetate) low‐profile additives on properties of cured unsaturated polyester resins. II. glass‐transition temperatures and mechanical properties

Three series of self‐synthesized poly(vinyl acetate)‐based low‐profile additives (LPAs), including poly(vinyl acetate), poly(vinyl chloride‐co‐vinyl acetate), and poly(vinyl chloride‐co‐vinyl acetate‐co‐maleic anhydride), with different chemical structures and molecular weights were studied. Their effects on the glass‐transition temperatures and mechanical properties for thermoset polymer blends made from styrene, unsaturated polyester, and LPAs were investigated by an integrated approach of the static phase characteristics, cured sample morphology, reaction kinetics, and property measurements. Based on Takayanagi mechanical models, the factors that control the glass‐transition temperature in each phase region of the cured samples and the mechanical properties are discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3347–3357, 2003     

Compatibility of low‐density polyethylene/poly(ethylene‐co‐vinyl acetate) binary blends prepared by melt mixing

The compatibility of low‐density polyethylene and poly(ethylene‐co‐vinyl acetate) containing 18 wt % vinyl acetate units (EVA‐18) was studied. For this purpose, a series of different blends containing 25, 50, or 75 wt % EVA‐18 were prepared by melt mixing with a single‐screw extruder. For each composition, three different sets of blends were prepared, which corresponded to the three different temperatures used in the metering section and the die of the extruder (140, 160, and 180°C), at a screw rotation speed of 42 rpm. Blends that contained 25 wt % EVA‐18 were also prepared through mixing at 140, 160, or 180°C but at a screw speed of 69 rpm. A study of the blends by differential scanning calorimetry showed that all the prepared blends were heterogeneous, except that containing 75 wt % EVA‐18 and prepared at 180°C. However, because of the high interfacial adhesion, a fine dispersion of the minor component in the polymer matrix was observed for all the studied blends with scanning electron microscopy. The tensile strengths and elongations at break of the blends lay between the corresponding values of the two polymers. The absence of any minimum in the mechanical properties was strong evidence that the two polymers were compatible over the whole range of composition. The thermal shrinkage of the blends at various temperatures depended mainly on the temperature and EVA‐18 content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 841–852, 2003     

Morphology,resistivity, and thermal behavior of EVOH/carbon black and EVOH/graphite composites prepared by simple saponification method

Poly(ethylene‐co‐vinyl alcohol) (EVOH)/carbon black (CB) and EVOH/graphite (GP) electro‐conductive composites were prepared by saponification of poly(ethylene‐co‐vinyl acetate) (EVA)/CB and EVA/GP composites in ethanol/KOH solution. The electrical resistivity change and positive temperature coefficient (PTC) behavior of these composites were investigated. The volume resistivity of EVA/CB and EVA/GP composites was decreased with saponification time. It can be observed that EVA/CB10 and EVA/GP05 composites showed a significant reduction in resistivity after saponification for 1 h. With the increase in saponification time, PTC peak temperature of both composites was shifted at a higher temperature. Tensile properties, morphology, and thermal behavior of the prepared composites have been also evaluated using universal test machine, scanning electron microscopy, and differential scanning calorimetry, respectively. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers