Miscible blends of poly(4‐vinyl phenol)/poly (trimethylene terephthalate)

A new miscible blend of all compositions comprising poly(4‐vinyl phenol) (PVPh) and poly(trimethylene terephthalate) (PTT) was discovered and reported. The blends exhibit a single composition‐dependent glass transition and homogeneous phase morphology, with no lower critical solution temperature (LCST) behavior upon heating to high temperatures. Interactions and spherulite growth kinetics in the blends were also investigated. The Flory–Huggins interaction parameter (χ₁₂) and interaction energy density (B) obtained from analysis of melting point depression are negative (χ₁₂ = ?0.74 and B = ?32.49 J cm^?3), proving that the PVPh/PTT blends are miscible over a wide temperature range from ambient up to high temperatures in the melt state. FTIR studies showed evidence of hydrogen‐bonding interactions between the two polymers. The miscibility of PVPh with PTT also resulted in a reduction in spherulite growth rate of PTT in the miscible blend. The Lauritzen–Hoffman model was used to analyze the spherulite growth kinetics, which showed a lower fold‐surface free energy (σ_e) of the blends than that of the neat PTT. The decrease in the fold‐surface free energy has been attributed to disruption of the PTT lamellae exerted by PVPh in an intimately interacted miscible state. Copyright © 2004 Society of Chemical Industry     

Preparation of poly(vinyl amine)‐grafted crosslinked poly(vinyl alcohol) microspheres

Crosslinked poly(vinyl alcohol) (CPVA) microspheres were first prepared via the suspension polymerization of vinyl acetate and the alcoholysis of poly(vinyl acetate). Afterwards, a two‐step method involving graft polymerization and Hofmann degradation was used to prepare functional poly(vinyl amine)‐grafted crosslinked poly(vinyl alcohol) (PVAm–CPVA) microspheres, onto which poly(vinyl amine) (PVAm) macromolecules were grafted. The graft polymerization of acrylamide (AM) on CPVA microspheres was performed with cerium salt as the initiator in an acidic aqueous medium, resulting in polyacrylamide (PAM)‐grafted CPVA microspheres. Subsequently, the grafted PAM was transformed into PVAm via the Hofmann degradation reaction, and PVAm–CPVA microspheres were prepared. The effects of the main factors on the graft polymerization and Hofmann degradation were examined, and the reaction mechanisms were researched in depth. The experimental results showed that for the graft polymerization of AM on CPVA microspheres initiated by cerium salt, the acid concentration and the amount of cerium salt affected the grafting degree of PAM greatly. For the Hofmann degradation reaction of the grafted PAM, the amination degree of PVAm–CPVA microspheres was obviously affected by the amount of sodium hypochlorite in the presence of sodium hydroxide. The preliminary adsorption tests showed that PVAm–CPVA microspheres were multifunctional and had strong adsorption ability for Fe(III) ions by chelation action and for chromate ions (CrO) by strong electrostatic interactions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Miscible blends containing bacterial poly(3‐hydroxyvalerate) and poly(p‐vinyl phenol)

The miscibility of poly(3‐hydroxyvalerate) (PHV)/poly(p‐vinyl phenol) (PVPh) blends has been studied by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. The blends are miscible as shown by the existence of a single glass transition temperature (T_g) and a depression of the equilibrium melting temperature of PHV in each blend. The interaction parameter was found to be −1.2 based on the analysis of melting point depression data using the Nishi–Wang equation. Hydrogen‐bonding interactions exist between the carbonyl groups of PHV and the hydroxyl groups of PVPh as evidenced by FTIR spectra. The crystallization of PHV is significantly hindered by the addition of PVPh. The addition of 50 wt % PVPh can totally prevent PHV from cold crystallization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 383–388, 1999     

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     

Miscibility and crystallization of biodegradable poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)/poly(vinyl phenol) blends

Miscibility and crystallization of biodegradable poly (3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) (PHBHHx)/poly(vinyl phenol) (PVPh) blends were investigated in this work. PHBHHx is miscible with PVPh over the whole composition range as evidenced by the single composition dependent glass transition temperature and the depression of equilibrium melting point of PHBHHx in the blends. The overall crystallization rates decrease with increasing crystallization temperature for both neat PHBHHx and its blends with PVPh; moreover, the overall crystallization rates are slower in the PHBHHx/PVPh blends than in neat PHBHHx at the same crystallization temperature. Blending with PVPh may change the crystallization mechanism of PHBHHx in the blends compared with that of neat PHBHHx. Both neat PHBHHx and the PHBHHx/PVPh blends exhibit a crystallization regime II to III transition. The crystal structure of PHBHHx is not modified in the PHBHHx/PVPh blends; however, the values of crystal layer thickness, amorphous layer thickness, and long period all become larger with increasing PVPh content in the blends. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Synthesis of poly(vinyl alcohol)‐graft‐poly(ε‐caprolactone) and poly(vinyl alcohol)‐graft‐poly(lactide) in melt with magnesium hydride as catalyst

Grafting of poly(ε‐caprolactone) (PCL) and poly(lactide) (PLA) chains on poly(vinyl alcohol) backbone (PVA degree of hydrolysis 99%) was investigated using MgH₂ environmental catalyst and melt‐grown ring‐opening polymerization (ROP) of ε‐caprolactone (CL) and L ‐lactide (LA), that avoiding undesirable toxic catalyst and solvent. The ability of MgH₂ as catalyst as well as yield of reaction were discussed according to various PVA/CL/MgH₂ and PVA/LA/MgH₂ ratio. PVA‐g‐PCL and PVA‐g‐PLA were characterized by ¹H‐ and ¹³C‐NMR, DSC, SEC, IR. For graft copolymers easily soluble in tetrahydrofuran (THF) or chloroform, wettability and surface energy of cast film varied in relation with the length and number of hydrophobic chains. Aqueous solution of micelle‐like particles was realized by dissolution in THF then addition of water. Critical micelle concentration (CMC) decreased with hydrophobic chains. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Crystallization kinetics and morphology of poly(butylene succinate)/poly(vinyl phenol) blend

Biodegradable crystalline poly(butylene succinate) (PBSU) can form miscible polymer blends with amorphous poly(vinyl phenol) (PVPh). The isothermal crystallization kinetics and morphology of neat and blended PBSU with PVPh were studied by differential scanning calorimetry (DSC), optical microscopy (OM), wide angle X-ray diffraction (WAXD), and small angle X-ray scattering (SAXS) in this work. The overall isothermal crystallization kinetics of neat and blended PBSU was studied with DSC in the crystallization temperature range of 80-88 °C and analyzed by applying the Avrami equation. It was found that blending with PVPh did not change the crystallization mechanism of PBSU, but reduced the crystallization rate compared with that of neat PBSU at the same crystallization temperature. The crystallization rate decreased with increasing crystallization temperature, while the crystallization mechanism did not change for both neat and blended PBSU irrespective of the crystallization temperature. The spherulitic morphology and growth were observed with hot stage OM in a wide crystallization temperature range of 75-100 °C. The spherulitic morphology of PBSU was influenced apparently by the crystallization temperature and the addition of PVPh. The linear spherulitic growth rate was measured and analyzed by the secondary nucleation theory. Through the Lauritzen-Hoffman equation, some parameters of neat and blended PBSU were derived and compared with each other including the nucleation parameter (K_g), the lateral surface free energy (σ), the end-surface free energy (σ_e), and the work of chain folding (q). Blending with PVPh decreased all the aforementioned parameters compared with those of neat PBSU; however, the decrease extent was limited. WAXD result showed that the crystal structure of PBSU was not modified after blending with PVPh. SAXS result showed that the long period of blended PBSU increased, possibly indicating that the amorphous PVPh might reside mainly in the interlamellar region of PBSU.     

Miscibility enhancement through hydrogen bonding interaction of biodegradable poly(3‐hydroxybutyrate) blending with poly(styrene‐co‐vinyl phenol) copolymer

Differential scanning calorimetry, one‐ and two‐dimensional Fourier transform infrared (FTIR), and solid state nuclear magnetic resonance (NMR) spectroscopy have been used to investigate the miscibility of and specific interactions between poly(styrene‐co‐vinyl phenol) (PSOH) and poly(3‐hydroxybutyrate) (PHB) upon varying the vinyl phenol content of the PSOH copolymer. The FTIR and solid state NMR spectra revealed that the phenol units of PVPh interact with the carbonyl groups of PHB through intermolecular hydrogen bonding. A miscibility window exists when the vinyl phenol fraction in the copolymer is greater than 22 mol % in the PSOH/PHB blend system, as predicted using the Painter–Coleman association model. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of electrorheological active ionomers from poly(2‐hydroxyethyl methacrylate)‐co‐poly(4‐vinyl pyridine)

In this study, synthesis, characterization, partial hydrolysis, and salt formation of poly(2‐hydroxyethyl methacrylate)‐co‐poly(4‐vinyl pyridine), (poly(HEMA)‐co‐poly‐(4‐VP)) copolymers were investigated. The copolymers were synthesized by free radical polymerization using K₂S₂O₈ as an initiator. By varying the monomer/initiator ratio, chain lengths of the copolymers were changed. The copolymers were characterized by gel permeation chromatography (GPC), viscosity measurements, ¹H and ¹³C NMR and FTIR spectroscopies, elemental analysis, and end group analysis methods. The copolymers were partially hydrolyzed by p‐toluene sulfonic acid monohydrate (PTSA·H₂O) and washed with LiOH_(aq) solution to prepare electrorheological (ER) active ionomers, poly(Li‐HEMA)‐co‐poly(4‐VP). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3540–3548, 2006     

Synthesis,characterization, and properties of poly(vinyl acetate)‐ and poly(vinyl alcohol)‐grafted chitosan

Graft copolymers of chitosan and vinyl acetate were synthesized by free radical technique using cerium (IV) as the initiator. Under controlled conditions, as much as 92% grafting with a grafting yield of 30–40% could be achieved. Chitosan‐g‐poly(vinyl alcohol) copolymers were derived by the alkaline hydrolysis of the chitosan‐g‐poly(vinyl acetate) precursor. Thermogravimetric, FTIR, and X‐ray diffraction analyses of chitosan and the copolymers confirmed the grafting reaction between chitosan and vinyl acetate and also the subsequent hydrolysis. Both the copolymers possessed very good film‐forming properties. Grafting resulted in a significant increase in mechanical strength of both the copolymers in the dry condition. Chitosan‐g‐poly(vinyl acetate) (CH‐PVAc) proved more hydrophobic than did pure chitosan, whereas chitosan‐g‐poly(vinyl alcohol) (CH‐PVOH) exhibited enhanced hydrophilicity as evident from their swelling characteristics and contact angle measurements. The enhanced swelling of CH‐PVOH was ascribed to the presence of the pendant poly(vinyl alcohol) group. At pH 1.98, the CH‐PVAc copolymer films showed greater stability than do pure chitosan films, which is highly beneficial for specific biomedical applications. Both the copolymers showed lower glass transition temperature than do pure chitosan. Grafting did not affect the overall thermal stability, and the differential thermogram substantiated the grafting. The investigations indicate that the synthetic–natural hybrid copolymers having desirable mechanical properties and tailored hydrophilic/hydrophobic characteristics are realizable. These polymers could be exploited for varied biomedical applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1852–1859, 2007     

Nonisothermal crystallization kinetics of biodegradable poly(butylene succinate)/poly(vinyl phenol) blend

Nonisothermal melt crystallization kinetics of biodegradable PBSU/PVPh blend was investigated with differential scanning calorimetry (DSC) from the viewpoint of practical application. PBSU/PVPh blends were cooled from the melt at various cooling rates ranging from 2.5 to 40°C/min. The crystallization peak temperature decreased with increasing the cooling rate for both neat and blended PBSU. Furthermore, the crystallization peak temperature of PBSU in the blend was lower than that of neat PBSU at a given cooling rate. Two methods, namely the Avrami equation and the Tobin method, were used to describe the nonisothermal crystallization of PBSU/PVPh blend. It was found that the Avrami equation was more suitable to predict the nonisothermal crystallization of PBSU/PVPh blend than the Tobin method. The effects of cooling rate and blend composition on the crystallization behavior of PBSU were studied in detail. It was found that the crystallization rate decreased with decreasing the cooling rate for both neat and blended PBSU. However, the crystallization of PBSU blended with PVPh was retarded compared with that of neat PBSU at the same cooling rate. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 972–978, 2007     

Release of salicylic acid through poly(vinyl alcohol)/poly(vinyl pyrrolidone) and poly(vinyl alcohol‐g‐N‐vinyl‐2‐pyrrolidone) membranes

A controlled release profile of salicylic acid (SA) for transdermal administration has been developed. Poly (vinyl alcohol) (PVA) and Poly(vinyl alcohol)/Poly(vinyl pyrrolidone) (PVP) blended preparations were used to prepare the membranes by solvent‐casting technique. The release of the drug from the membranes was evaluated at in vitro conditions. The effects of PVA/PVP (v/v) ratio, pH, SA concentration and temperature were investigated. 60/40 (v/v) PVA/PVP ratio was found to be the best ratio for the SA release. Increase in pH and temperature was observed to increase the transport of SA. Instead of blending PVA with PVP, N‐Vinyl‐2‐pyrrolidone (VP) was grafted onto the PVA and the delivery performance for SA was compared with that of the blended PVA/PVP membranes. Grafted membranes gave higher transport percentages than the blended membranes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1244–1253, 2006     

Preparation and properties of blends from poly(3‐hydroxybutyrate) with poly(vinyl acetate)‐modified starch

This research used the ceric ion to initiate the graft‐polymerization of vinyl acetate (VAc) to a soluble potato starch. Fourier transform infrared spectra confirmed the formation of starch graft copolymer. After 4 h of reaction at 50°C, total monomer conversion, grafting efficiency, and grafting ratio were measured as 91%, 12.5%, and 0.223, respectively. The synthesized PVAc‐modified starch was then blended with poly(3‐hydroxybutyrate) (PHB). Structures, thermal and mechanical properties of the prepared blends were examined. The results showed the PHB and PVAc‐modified starch were miscible in all compositions. In addition, thermal gravimetric analysis revealed that the addition of PVAc‐modified starch increased the thermal stability of the PHB component. Further evidence also showed that the addition of PVAc‐modified starch reduced the extent of decrease in molecular weight of PHB in a melt‐mixer. PHB/PVAc‐modified starch blends exhibit higher toughness than pure PHB because of increased compatibility and the leathery PVAc‐modified starch. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Electrospinning of poly(vinyl alcohol) and poly(4‐styrenesulfonic acid) for fuel cell applications

Electrospun fibers of poly(vinyl alcohol) (PVA) and PVA/poly(4‐styrenesulfonic acid) (PSSA) were obtained. By varying PVA to PSSA weight ratios, various fiber sizes and shapes were observed. The fiber diameters ranged from 176 to 766 nm, and the largest fibers were obtained from 15 wt % aqueous PVA solution. The effect of solution viscosity on fiber morphology was discussed. The presence of PSSA in electrospun fibers was confirmed by Fourier Transform Infrared spectroscopy. The PVA fibers were thermally stable up to 250°C, and the PVA/PSSA fibers were stable up to approximately 150°C. The water stability of the fibers was improved by heat‐treatment at 120°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Engineering properties of poly(vinyl chloride)–poly(butyl methacrylate) semi‐1 and semi‐2 interpenetrating polymer networks

Semi‐1 and semi‐2 interpenetrating polymer networks (IPNs) of poly(vinyl chloride) (PVC) and in situ formed poly(butyl methacrylate) (PBMA) have been synthesized using diallyl phthalate and ethylene glycol dimethacrylate as the crosslinkers of PVC and PBMA, respectively. These were then characterized with reference to their mechanical, thermal, and morphological properties. The mechanical and thermal characteristics revealed modification over the unmodified polymeric systems in relation to their phase morphologies. The semi‐1 IPNs displayed a decrease in their mechanical parameters of modulus and UTS while semi‐2 IPNs exhibited a marginal increase in these two values. The semi‐1 IPNs, however, also revealed a decrease in the elongation and toughness values away from the normal behavior. The thermomechanical behavior of both the systems is in conformity with their mechanicals in displaying the softening characteristics of the system and stabilization over unmodified PVC. The DSC thermograms are also correlated to these observations along with the heterogeneous phase morphology which is displayed by both the systems especially at higher concentration of PBMA incorporation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Nonisothermal cure kinetics of diglycidylether of bisphenol‐A/amine system reinforced with nanosilica particles

Epoxy‐silica nanocomposites were obtained from directly blending diglycidylether of bisphenol‐A (DGEBA)‐based epoxy and nanoscale silica (NS) and then curing with 4,4′‐diaminodiphenylamine (DDA). The effect of amount of nanosilica (NS) particles as catalyst on the mechanism and kinetic parameters of cure reaction of DGEBA/DDA system was studied. The kinetics parameters were obtained from nonisothermal differential scanning calorimeter (DSC) data using the Kissinger and Ozawa equations. The exothermic peak was shifted toward lower temperatures in DGEBA/DDA/NS system with increasing the amount of nanoslica particles. However, the existence of NS particles with hydroxyl groups in the structure in the mixture of DGEBA/DDA catalyzes the cure reaction and increases the rate constant. The activation energy of cure reaction of DGEBA/DDA system obtained from two methods were in good agreement, and showed a decrease when NS particles were present in the mixture. The mechanism of reaction of DGEBA with DDA was carried out by isothermal curing in the oven at 130°C and measuring the disappearance peak of epoxide group at 916 cm^?1 using FTIR. The diffusive behavior of two systems was investigated during water sorption at 25°C and the experimental results fitted well to Fick's law. Diffusion coefficient of cured sample from DGEBA/DDA/10% NS blend decreased in comparison with the sample without NS particles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3855–3863, 2007     

Influence of molecular interactions on spherulite morphology in miscible poly(ethylene oxide)/epoxy network versus poly(ethylene oxide)/poly(4‐vinyl phenol) blend

Relationships between the spherulite morphology and changes in hydrogen‐bonding interactions between the linear poly(ethylene oxide) (PEO) polymer and a crosslinking epoxy system (diglycidylether of bisphenol‐A resin with 4,4′‐diaminodiphenylsulfone) (DGEBA/DDS) before and after cure have been explored The hydrogen‐bonding interaction is more significant before cure because of the interactions between the ether group of PEO and the amine group of DDS. The interaction between PEO and epoxy/DDS becomes less in the cured network. The morphology of the PEO crystals is, in turn, affected by the contents and chemical structures (functional groups, molecular weights, crosslinks, etc) of crosslinking epoxy/DDS. PEO/poly(4‐vinyl phenol) (PVPh), a thermoplastic non‐curing miscible system with the hydrogen bonding between the ether group of PEO and the ? OH group of PVPh, is also compared. In comparison with the PEO/epoxy/DDS system, the spherulite morphology of PEO/PVPh becomes more extensively spread out, with the extents increasing with the PVPh contents in the PEO/PVPh blend. © 2001 Society of Chemical Industry