Reactive blending of poly(L‐lactic acid) with poly(ethylene‐co‐vinyl alcohol)

Poly(L ‐lactic acid) (PLLA) was blended with poly(ethylene‐co‐vinyl alcohol) (EVOH) in the presence of an esterification catalyst to induce reaction between the hydroxyl groups of EVOH and the terminal carboxylic group of PLLA. Nascent low‐molecular‐weight PLLA, obtained from a direct condensation polymerization of L ‐lactic acid in bulk state, was used for the blending. Domain size of the PLLA phase in the graft copolymer was much smaller than that corresponding to a PLLA/EVOH simple blend. The mechanical properties of the graft copolymer were far superior to those of the simple blend, and the graft copolymer exhibited excellent mechanical properties even though the biodegradable fraction substantially exceeded the percolation level. The grafted PLLA reduced the crystallization rate of the EVOH moiety. Melting peak temperature (T_m) of the PLLA phase was not observed until the content of PLLA in the graft reaction medium went over 60 wt %. The modified Sturm test results demonstrated that biodegradation of EVOH‐g‐PLLA took place more slowly than that of an EVOH/PLLA simple blend, indicating that the chemically bound PLLA moiety was less susceptible to microbial attack than PLLA in the simple blend. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 886–890, 2005     

Melting behavior and surface morphology of poly(vinyl acetate‐co‐vinyl alcohol) copolymer

In a study of the surface morphology of commercial poly(vinyl acetate‐co‐vinyl alcohol) (ACA copolymer) with different percents of hydrolysis, different structures like fibrils, spherulites, micelles, vesicles, and spheroids were seen. The copolymer was crystallized by annealing at two different temperatures. The morphology of the polymer after crystallization and also without crystallization was studied. A decrease in the melting temperature just by heating to the melting temperature was observed, and for a detailed study, repetitive heating of the copolymer was carried out and changes in the mass and heat of fusion after every heating was recorded. The morphology of the copolymer after repetitive heating was studied. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1211–1218, 2002     

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     

Synthesis and properties of carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide) as a novel cellulose‐based superabsorbent

A new cellulose‐based superabsorbent polymer, carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide), was prepared by the free‐radical grafting solution polymerization of acrylic acid (AA) and acrylamide (AM) monomers onto carboxymethyl cellulose (CMC) in the presence of N,N′‐methylenebisacrylamide as a crosslinker with a redox couple of potassium persulfate and sodium metabisulfite as an initiator. The influences of reaction variables such as the initiator content, crosslinker content, bath temperature, molar ratio of AA to AM, and weight ratio of the monomers to CMC on the water absorbency of the carboxymethylcellulose‐graft‐poly(acrylic acid‐co‐acrylamide) copolymer were investigated. The copolymer's structures were characterized with Fourier transform infrared spectroscopy. The optimum reaction conditions were obtained as follows: the bath temperature was 50°C; the molar ratio of AA to AM was 3 : 1; the mass ratio of the monomers to CMC was 4 : 1; and the weight percentages of the crosslinker and initiator with respect to the monomers were 0.75 and 1%, respectively. The maximum water absorbency of the optimized product was 920 g/g for distilled water and 85 g/g for a 0.9 wt % aqueous NaCl solution. In addition, the superabsorbent possessed good water retention and salt resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1382–1388, 2007     

Antifungal effect of carbendazim supported on poly(ethylene‐co‐vinyl alcohol) and epoxy resin

Ethylene‐vinyl alcohol copolymers (EVOH) were prepared by the conventional saponification of poly(ethylene‐co‐vinyl acetate) using a solution of potassium hydroxide in ethanol. An organic fungicide, consisting of a 2‐benzimidazole carbamoyl (CBZ) group supported on EVOH (EVOH‐CBZ), was prepared by the transesterification reaction of methyl 2‐benzimidazole cabamate (carbendazim) with EVOH. The antifungal activity of the synthesized polymers was examined by the halo zone test against Aspergillus fumigatus and Penicillium pinophilum. The synthesized EVOH‐CBZ complex showed a strong antifungal activity. The bound CBZ units were susceptible to hydrolysis. CBZ bonded to an epoxy resin precursor, diglycidyl ether of bisphenol A (DGEBA‐CBZ), retained its antifungal activity, which was somewhat weaker in comparison with that of EVOH‐CBZ. When the DGEBA‐CBZ complex was crosslinked by isophoronediamine, the antifungal activity disappeared almost completely, indicating that it is necessary for the CBZ units to release from their polymer supports to have the antifungal effects. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 728–736, 2001     

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     

The effectiveness of magnesium carbonate‐based flame retardants for poly(ethylene‐co‐vinyl acetate) and poly(ethylene‐co‐ethyl acrylate)

In this report we outline recent work on the evaluation of magnesium carbonate‐based flame retardants for polymers commonly used in halogen‐free flame retardant wire and cable applications: poly(ethylene‐co‐vinyl acetate) (EVA) and poly(ethylene‐co‐ethyl acrylate) (EEA). Natural magnesium carbonate (magnesite), synthetic magnesium carbonate (hydromagnesite), and hydromagnesite/huntite blends were combined with EVA or EEA and tested for flame retardancy effectiveness with the cone calorimeter. The flammability results showed that the effectiveness of these carbonates was polymer dependent, suggesting that polymer degradation chemistry played a role in the flammability reduction mechanism. Hydromagnesites were, in general, more effective in reducing flammability, being comparable in performance to magnesium hydroxide. Finally, we report some polymer–clay (organically treated montmorillonite and magadiite) + magnesium carbonate flame retardant results which showed that the nanocomposite yielded mixed results. Specifically, the polymer–clay nanocomposite samples did not always yield the greatest reductions in peak heat release rate. Copyright © 2007 John Wiley & Sons, Ltd.     

Formation of porous poly(ethylene‐co‐vinyl alcohol) membrane via thermally induced phase separation

Crystalline poly(ethylene‐co‐vinyl alcohol) (EVOH) membranes were prepared by a thermally induced phase separation (TIPS) process. The diluents used were 1,3‐propanediol and 1,3‐butanediol. The dynamic crystallization temperature was determined by DSC measurement. No structure was detected by an optical microscope in the temperature region higher than the crystallization temperature. This means that porous membrane structures were formed by solid–liquid phase separation (polymer crystallization) rather than by liquid–liquid phase separation. The EVOH/butanediol system showed a higher dynamic crystallization temperature and equilibrium melting temperature than those of the EVOH/propanediol system. SEM observation showed that the sizes of the crystalline particles in the membranes depended on the polymer concentration, cooling rate, and kinds of diluents. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2449–2455, 2001     

Effect of plasticizers in poly(vinyl alcohol)‐based hybrid solid polymer electrolytes

Hybrid solid polymer electrolyte films consisting of poly(vinyl alcohol) (PVA), poly(methyl methacrylate) (PMMA), LiBF₄, and ethylene carbonate/propylene carbonate (EC/PC) were prepared with a solvent‐casting technique. The complexation was investigated with Fourier transform infrared and X‐ray diffraction. The ionic conductivities of the electrolyte films were determined with an alternating‐current impedance technique for various temperatures in the range of 302–373 K. The maximum conductivity value, 1.2886 × 10^?3 S/cm, was observed for a PVA–PMMA–LiBF₄–EC complex. Thermogravimetry/differential thermal analysis was performed to ascertain the thermal stability of the electrolyte with the maximum conductivity value. For an examination of the cyclic and reversible performance of the film, a cyclic voltammetry study was carried out. The surface morphology of the EC‐and PC‐based electrolytes was examined with scanning electron microscopy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2794–2800, 2003     

Temperature effect on the infrared absorption of ferroelectric copolymer poly(vinylidene fluoride‐trifluoroethylene)

The intensity of two infrared absorption bands of annealed ferroelectric copolymers [poly(vinylidene fluoride‐trifluoroethylene)] in the mid‐infrared high‐frequency region was found to be strongly related to the annealing temperature. The vibration modes in the amorphous phase of the copolymers were considered to account for these two bands. On the other hand, the temperature dependence of the absorption spectra of the copolymers in the heating and cooling cycle was investigated. In the vicinity of the Curie transition, the absorption bands associated with the CH₂ vibrations exhibited a shift in frequency. Two bands were identified as shifting to a high frequency, and one band shifted to a low frequency with heating. These three bands were restored to their room‐temperature frequency with cooling. In addition, copolymers of a higher vinylidene fluoride content exhibited a more pronounced thermal hysteresis in terms of a shift in frequency. This was consistent with the electrical behavior of the copolymers. The trends of the frequency shifts suggested that dipole–dipole coupling existed between two adjacent chains in the all‐trans conformation, which originated from the interaction of the CH₂ and CF₂ dipoles. The coupling diminished as the copolymers underwent a change in phase above the transition temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1662–1666, 2005     

Morphological control of porous ethylene‐vinyl acetate copolymer membrane obtained from a co‐continuous ethylene‐vinyl acetate copolymer/poly(ϵ‐caprolactone) blend

Ethylene‐vinyl acetate copolymer (EVA)/poly(?‐caprolactone) (PCL) blend (50/50 w/w) with co‐continuous morphology was prepared via melt mixing for fabricating microporous EVA membrane materials through selective solvent extraction. Shear flow and quiescent annealing techniques were employed to control co‐continuous phase size in the EVA/PCL blend, and the time‐ and temperature‐dependent relations of phase size were then evaluated theoretically. Using these techniques, microporous EVA membrane materials with various pore sizes ranging from 2 µm to more than 200 µm were obtained. In contrast to the porous EVA membrane prepared by the traditional way of solvent casting/particulate leaching, the as‐obtained microporous membrane shows a higher level of interconnectivity and much narrower pore size distribution with uniform pore structure. © 2013 Society of Chemical Industry     

Electrochemical synthesis and corrosion protection properties of poly(o‐toluidine) coatings on low carbon steel

Uniform and strongly adherent poly(o‐toluidine) (POT) coatings have been synthesized on low carbon steel (LCS) substrates by electrochemical polymerization (ECP) of o‐toluidine under cyclic voltammetric conditions from an aqueous sodium tartrate solution. Cyclic voltammetry (CV), UV‐visible absorption spectroscopy, Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD) measurements, and scanning electron microscopy (SEM) were used to characterize these coatings, which indicates that the sodium tartrate is a suitable medium for the ECP of o‐toluidine and it occurs without noticeable dissolution of LCS. Corrosion protection properties of the POT coatings were evaluated in aqueous 3% NaCl by the potentiodynamic polarization measurements and CV. The result of the potentiodynamic polarization demonstrates that the POT coating has ability to protect the LCS against corrosion. The corrosion potential was about 334 mV more positive in aqueous 3% NaCl for the POT‐coated LCS than that of bare LCS and reduces the corrosion rate of LCS almost by a factor of 50. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 685–695, 2005     

Immobilization of catalase onto hydrophilic mesoporous poly(ethylene‐co‐vinyl alcohol) monoliths

Poly(ethylene‐co‐vinyl alcohol) monoliths have been fabricated by a thermally induced phase separation method. Catalase was immobilized onto the monolith surfaces after activating the hydroxyl groups of the monolith in the presence of carbonyldiimidazole. The immobilized catalase exhibited the same optimum pH and temperature values to those of the free catalase. In addition, the immobilized catalase showed better thermal stability and high reusability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42556.     

Interpolymer interactions and miscibility in poly(n‐butyl methacrylate‐co‐methacrylic acid)/poly(styrene‐co‐N,N‐dimethyl acrylamide) blends

The miscibility of poly(n‐butyl methacrylate‐co‐methacrylic acid) containing 18 mol % methacrylic acid (BMAM‐18) and poly(styrene‐co‐N,N‐dimethyl acrylamide) containing 17 mol % N,N‐dimethyl acrylamide (SAD‐17) was investigated with viscometry, differential scanning calorimetry (DSC), and Fourier transform infrared (FTIR) spectroscopy. The DSC analysis showed a single glass‐transition temperature for all the blends, indicating that these copolymers were miscible over the entire composition range. The glass‐transition temperatures of these blends were higher than those calculated with the additivity rule. This was characteristic of the presence of specific interactions. The interactions between BMAM‐18 and the tertiary amide of SAD‐17 were studied with FTIR spectroscopy, which revealed that hydrogen‐bonding interactions occurred between the hydroxyl groups of BMAM‐18 and the carbonyl amide of SAD‐17. A new band characterizing these interactions appeared around 1613 cm^?1. The quantitative results showed that the fraction of the associated amide increased with an increase in the amount of the acidic BMAM‐18 copolymer. Although BMAM‐18 and SAD‐17 led to homogeneous solutions in butan‐2‐one, as the concentration of N,N‐dimethyl acrylamide increased to 32 mol % [as within the poly(styrene‐co‐N,N‐dimethyl acrylamide) containing 32 mol % N,N‐dimethyl acrylamide], complexation occurred when this latter compound was mixed with BMAM‐18 in butan‐2‐one. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2717–2724, 2006     

Foaming of poly(ethylene‐co‐vinyl acetate) and poly(ethylene‐co‐vinyl acetate‐co‐carbon monoxide) and their blends with carbon dioxide

Poly(ethylene‐co‐vinyl acetate) (EVA‐25) and poly(ethylene‐co‐vinyl acetate‐co‐carbon monoxide) (EVACO‐2410) and their blends with EVACO:EVA ratios of 80:20, 60:40, 40:60, and 20:80 were foamed using CO₂. These foams are of interest for applications ranging from footwear to medical devices. Foaming experiments were carried out using 1 mm thick melt‐extruded films in CO₂ at a range of pressures (100, 200, and 300 bar) and temperatures (30, 40, 50, and 60 °C). Foamability of the polymers was explored both under isothermal and gradient temperature conditions. Foams of EVACO‐2410 displayed high initial expansions followed by postfoaming relaxation and shrinkage while foams generated from EVA‐25 showed more dimensional stability. Blending EVACO‐2410 with EVA‐25 was explored as an approach to reduce postfoaming relaxation and shrinkage. The surfaces of the foamed samples displayed blistering that was linked to CO₂ bubble entrapment and coalescence at the surface. Scanning electron micrographs of the foams generated from blends displayed distinct morphologies reflecting whether the sections were representing the machine‐ or cross‐machine direction of extruded films. In going from EVACO‐2410 to EVA‐25, the cell densities ranged from about 10⁶ to 10¹⁰ cells/cm³. Foams with low bulk densities of about 0.11 g/cm³ could be generated. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45841.     

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     

Preparation of poly(vinyl alcohol) films with promising physical properties in comparison with commercial polyethylene film

Poly(vinyl alcohol) (PVA) films with different thicknesses (0.08, 0.2, 0.23, 0.42 mm) were prepared by a casting technique. The transmission and the absorption of the PVA films were measured as functions of the wavelengths. PVA film with a thickness of 0.42 mm showed zero transmission in the wavelength range of 190–350 nm. The transmission spectrum of a commercial polyethylene film with a thickness of 0.21 mm was compared to the transmission spectrum of PVA film with a thickness of 0.42 mm. A correlation was found between the two transmission spectra in the region 190–350 nm and a 20% increase in the transmission of the PVA film in comparison with the transmission of commercial polyethylene in the region 350–1500 nm. The near‐infrared region of the transmission of commercial polyethylene was increased by 15% with respect to the transmission of the PVA film. The stress–strain measurements were done for PVA and commercial polyethylene films. The Young's modulus and the strength at break for PVA films are higher by two orders of magnitude than those for commercial polyethylene film. The strain at break for commercial polyethylene is 17% lower than that for PVA film. Radiation effects on the optical properties of PVA and commercial polyethylene films were investigated. The PVA and commercial polyethylene films were irradiated with a xeon arc lamp at 3.5–5 W/cm². The optical properties for PVA and commercial polyethylene films were studied after irradiation. The obtained results showed that PVA film with a thickness of 0.42 mm gave promising properties which could be used in technological applications. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1219–1226, 2002     

Effect of posttreatment on morphology and properties of poly(ethylene‐co‐vinyl alcohol) microporous hollow fiber via thermally induced phase separation

Poly(ethylene‐co‐vinyl alcohol) (EVOH) hollow fiber membranes were prepared by thermally induced phase separation (TIPS) process. Water, methanol, and acetone were used to extract the diluents in the fibers, respectively. Bigger shrinkage of fibers during extractant evaporation was observed when water or methanol was used. Their interaction parameters with EVOH were calculated via Hansen solubility, respectively. The mechanism of hollow fiber volume shrinkage was discussed. It was found that affinity of the extractant with polymer was the critical factor except for the surface tension of extractant. Through the X‐ray diffraction analysis during extraction and evaporation, the crystallization behavior of the polymer was studied. From the SEM photos, it was observed that the volume shrinkage was derived from the collapse of porous structure. The fiber sample extracted by acetone had similar morphology with the sample freeze‐dried. The gas and water permeability were also measured and the results were coincident with the morphology of fibers and shrinkage data. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4106–4112, 2007     

Effects of ethylene content of poly(ethylene‐co‐vinyl alcohol) on diameter of fibers produced by melt‐electrospinning

Rodlike samples were made from four kinds of poly(ethylene‐co‐vinyl alcohol) (EVAL) pellets with different ethylene contents. From these rodlike samples, fibers were produced using a melt‐electrospinning system equipped with a CO₂‐laser melting device. The effects on the fiber diameter of the ethylene content and the moisture regain of the rodlike samples were investigated. Furthermore, the physical properties of the fibers were investigated. The following conclusions were reached: (i) EVAL fibers having an average fiber diameter smaller than 1 μm can be obtained using the system developed; (ii) the diameter of EVAL fiber is influenced by the ethylene content and the moisture regain of the starting rods; (iii) the laser heating does not greatly decrease the melting point and the molecular weight of EVAL; and (iv) preferred crystal orientation can be seen in electrospun EVAL fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1368–1375, 2007     

Melt electrospinning from poly(L‐lactide) rods coated with poly(ethylene‐co‐vinyl alcohol)

Rodlike poly(L ‐lactide) (PLLA) samples coated with poly(ethylene‐co‐vinyl alcohol) (EVOH) were made. Fibers were produced from these rodlike samples by using a melt electrospinning system equipped with a laser irradiating device, and the effects of EVOH content and the processing parameters of the melt electrospinning on fiber diameters were investigated. We also studied the fiber formation mechanism from the rods during the laser melt electrospinning process. The following conclusions were reached: (i) coating of EVOH on PLLA rods has a remarkable effect on decreasing fiber diameter from 3 μm to around 1 μm; (ii) increases in the electric field strength and temperature of spinning space decrease the average diameter of fibers produced from pure PLLA rods, and longer collector distance leads to lager PLLA fiber diameter; and (iii) the migration of PLLA component from the core to the surface of electrospun fibers takes place during the fiber formation process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009