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     

Influence of solvent on size of poly(p‐oxybenzoyl) whiskers prepared from p‐acetoxybenzoic acid

Poly(p‐oxybenzoyl) (POB) crystals are prepared by the polymerization of p‐acetoxybenzoic acid (p‐ABA) at 320°C in various solvents to clarify the influence of miscibility between oligomer and solvent on the morphology as well as the size of the crystal. Concerning the morphology, whiskers are formed in less miscible solvents such as liquid paraffin and Barrel process oil B27. On the other hand, bundle‐like aggregates of fibrillar crystals tend to be formed in the solvents having higher miscibility such as Therm S 900 and 800, which are aromatic heat exchange media. Further, the solvents having higher temperature at which p‐ABA is completely dissolved during polymerization (T_s) yield a larger number of the whiskers with smaller width. The higher supersaturation of oligomers in less miscible solvents causes the formation of a larger number of nuclei with smaller size. Bundle‐like aggregates are formed in the solvents whose T_s is lower than 140°C by the fibrillation of pillar‐like crystals during polymerization owing to the reorganization. This shows a clear relationship between the width and T_s, and between the number of the crystals and T_s. Hence, the size of the whisker such as the length and the width can be predicted by the calculation with T_s, which is very valuable for the preparation of POB whiskers for use as industrial materials. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1129–1136, 2003     

Enhanced hydrolytic stability of poly(p‐dioxanone) with polycarbodiimide

The effect of polycarbodiimide (PCD) on hydrolytic stability of poly(p‐dioxanone) (PPDO) was investigated by hydrolytic degradation of PPDO and PPDO added with PCD (PPDOCD) in phosphate buffer solution (pH = 7.4) at 37°C. The variation of weight, water absorption, pH, molecular weight, tensile properties, surface morphologies, and thermal properties with degradation time were evaluated. After 11 weeks, the weight loss and water absorption of PPDO was 24 and 30%, respectively, but the corresponding values were only 3 and 5% for PPDOCD5, where 5 represents the weight percentage of PCD added; the molecular weight of PPDO decreased much faster than that of PPDOCD. The pH of the solution was monitored for 15 weeks and a final pH value of the solution involving PPDOCD5 was 6.81 whereas that of PPDO solution was 3.77, indicating that more acid fragments from PPDO samples migrate into the buffer solution. Surface morphological changes showed a better physical integrity for PPDOCD samples and they also kept their mechanical properties for a longer time than PPDO samples. These results revealed that PCD can retard the hydrolysis degradation of PPDO and enhance its hydrolytic stability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of poly(4‐aminophenol) by horseradish peroxidase and the evaluation of its adsorptivity for silver ions

In this study, poly(4‐aminophenol) was successfully prepared by an enzymatic reaction in water, with its molecular weights ranging from 12,000 to 52,000. The polymerization of 4‐aminophenol produced high yields over a wide pH ranging from 4 to 10. In addition, poly(4‐aminophenol) was also used for silver‐ion adsorption because it was composed of amino and hydroxyl groups. We found that the adsorption capacity of poly(4‐aminophenol) was relevant to the time, pH value, temperature, and concentration of silver ions, and the greatest adsorption capacity of poly(4‐aminophenol) for silver ions was 220 mg/g. Moreover, a series of tests showed that the adsorption of silver ions was mainly achieved by a reduction reaction, and the silver nanoparticles were formed with a face‐centered cubic structure, and their average particle size was about 10 nm. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40367.     

Synthesis and light‐emitting properties of a novel π‐conjugated poly[di(p‐phenyleneethynylene)‐alt‐ (p‐phenylenecyanovinylene)] containing n‐octyloxy side branches

A novel π‐conjugated poly[di(p‐phenyleneethynylene)‐alt‐(p‐phenylenecyanovinylene)] having n‐octyloxy side chains (PPE‐C₈PPE‐PPV) was prepared by polymerization of the monomer DEDB with BCN. Chemical structure of the polymer obtained was confirmed by ¹H NMR, FTIR, and EA. PPE‐C₈PPE‐PPV had a molecular weight enough to fabricate the electroluminescent (EL) device, and showed a good organosolubility, excellent thermal stability, and film‐forming property. In UV absorption and PL spectra in film it showed a maximum at 430 and 543 nm, respectively, which appeared 5 and 41 nm longer wavelengths than that of the solution, respectively. HOMO, LUMO energy levels and band gap were determined to be ?5.70, ?3.29, and 2.41 eV, respectively. Two EL devices with low‐work function cathodes were fabricated with the structures of ITO/PEDOT/PPE‐C₈PPE‐PPV/cathodes (LiF/Al and Mg:Ag/Ag). The both devices exhibited a bright green light emission at 545 nm and the maximum luminescence of 197 cd/cm² (LiF/Al) and 158 cd/cm² (Mg:Ag/Ag). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

ABA triblock copolymers from poly(p‐dioxanone) and poly(ethylene glycol)

Poly(p‐dioxanone)–poly(ethylene glycol)–poly(p‐dioxanone) ABA triblock copolymers (PEDO) were synthesized by ring‐opening polymerization from p‐dioxanone using poly(ethylene glycol) (PEG) with different molecular weights as macroinitiators in N₂ atmosphere. The copolymer was characterized by ¹H NMR spectroscope. The thermal behavior, crystallization, and thermal stability of these copolymers were investigated by differential scanning calorimetry and thermogravimetric measurements. The water absorption of these copolymers was also measured. The results indicated that the content and length of PEG chain have a greater effect on the properties of copolymers. This kind of biodegradable copolymer will find a potential application in biomedical materials. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1092–1097, 2006     

Nucleation effect of hydroxyl‐purified multiwalled carbon nanotubes in poly(p‐phenylene sulfide) composites

To investigate the nucleation effect of hydroxyl‐purified multiwalled carbon nanotubes (MWNTs‐OH) in poly(p‐phenylenesulfide) (PPS), a series of composites were prepared by blending PPS with MWNTs‐OH at 1, 2, and 3 wt %, respectively. Under SEM observation MWNTs‐OH were found homogeneously dispersed in the PPS matrix. DSC thermograms revealed that the enthalpy (ΔH_c) of the composites increased with increasing MWNT‐OH content, whereas the crystallization temperature (T_c) decreased progressively. The decrease in T_c was in accordance with the smaller crystallite size determined with WXRD characterization, and the increase in ΔH_c was evidenced by FTIR and XPS analyses. The higher ΔH_c shows that MWNTs‐OH serves as a nucleating agent, providing sufficiently multiplied sites for crystal growth. The lowering of T_c was attributed not only to MWNTs‐OH network hindrance to PPS chain fusing rearrangement, but also to a poorer affinity between MWNTs‐OH and PPS; both effects coordinately govern T_c of PPS/MWNTs‐OH composites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermal properties and non‐isothermal crystallization behavior of biodegradable poly(p‐dioxanone)/poly(vinyl alcohol) blends

Blends of two biodegradable semicrystalline polymers, poly(p‐dioxanone) (PPDO) and poly(vinyl alcohol) (PVA) were prepared with different compositions. The thermal stability, phase morphology and thermal behavior of the blends were studied by using thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). From the TGA data, it can be seen that the addition of PVA improves the thermal stability of PPDO. DSC analysis showed that the glass transition temperature (T_g) and the melting temperature (T_m) of PPDO in the blends were nearly constant and equal to the values for neat PPDO, thus suggesting that PPDO and PVA are immiscible. It was found from the SEM images that the blends were phase‐separated, which was consistent with the DSC results. Additionally, non‐isothermal crystallization under controlled cooling rates was explored, and the Ozawa theory was employed to describe the non‐isothermal crystallization kinetics. Copyright © 2006 Society of Chemical Industry     

Crystallization study on absorbable poly(p‐dioxanone) polymers by differential scanning calorimetry

An investigation was carried out on the crystallization behavior of p‐dioxanone polymers using differential scanning calorimetry (DSC). Kinetic analyses were performed on data collected primarily during isothermal crystallization. Isothermal data were treated within the framework of the classical Avrami equation. Using this approach, both the Avrami exponent, n, and the crystallization half‐time, t_1/2, were evaluated and their implications are discussed for each system studied. It is shown that a small change in the polymer's composition greatly affects the crystallization kinetics, as well as the crystallizability of the materials. Additionally, nonisothermal crystallization under controlled heating and cooling rates was explored. In the case of cooling from the melt, the Ozawa theory and the recently proposed Calculus method were employed to describe the nonisothermal crystallization kinetics. In view of our results, the validity of these two estimation techniques for determining important kinetic and morphological parameters is also discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 742–759, 2001     

Crystallization and melting behavior of poly(p‐phenylene sulfide) in blends with poly(ether sulfone)

Crystallization and melting behaviors of poly(p‐phenylene sulfide) (PPS) in blends with poly(ether sulfone) (PES) prepared by melt‐mixing were investigated by differential scanning calorimetry (DSC). The blends showed two glass transition temperatures corresponding to PPS‐ and PES‐rich phases, which increased with increasing PES content, indicating that PPS and PES have some compatibility. The cold crystallization temperature of the blended PPS was a little higher than that of pure PPS. Also, the heats of crystallization and melting of the blended PPS decreased with increasing PES content, indicating that the degree of crystallinity decreased with an increase of PES content. The isothermal crystallization studies revealed that the crystallization of PPS is accelerated by blending PPS with 10 wt % PES and further addition results in the retardation. The Avrami exponent n was about 4 independent on blend composition. The activation energy of crystallization increased by blending with PES. The equilibrium melting point decreased linearly with increasing PES content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1686–1692, 1999     

Conducting composites of poly(N‐vinylcarbazole), polypyrrole,and polyaniline with 13X‐zeolite

N‐vinylcarbazole (NVC) was polymerized by 13X zeolite alone in melt (65°C) or in toluene (110°C) and a poly(N‐vinylcarbazole) (PNVC)‐13X composite was isolated. Composites of polypyrrole (PPY) and polyaniline(PANI) with 13X zeolite were prepared via polymerization of the respective monomers in the presence of dispersion of 13X zeolite in water (CuCl₂ oxidant) and in CHCl₃ (FeCl₃ oxidant) at an ambient temperature. The composites were characterized by Fourier transform infrared analyses. Scanning electron microscopic analyses of various composites indicated the formation of lumpy aggregates of irregular sizes distinct from the morphology of unmodified 13X zeolite. X‐ray diffraction analysis revealed some typical differences between the various composites, depending upon the nature of the polymer incorporated. Thermogravimetric analyses revealed the stability order as: 13X‐zeolite > polymer‐13X‐zeolite > polymer. PNVC‐13X composite was essentially a nonconductor, while PPY‐13X and PANI‐13X composites showed direct current conductivity in the order of 10^?4 S/cm in either system. However, the conductivity of PNVC‐ 13X composite could be improved to 10^?5 and 10^?6 S/cm by loading PPY and PANI, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 913–921, 2006     

Synthesis and electrical properties of copolymers of o‐phenylenediamine with aniline, 3,4‐ethylenedioxythiophene and 2,3,5,6‐tetrafluoroaniline

Copolymers (P(PDA/Ar)) of o‐phenylenediamine with aniline (Ar = ANi), 3,4‐ethylenedioxythiophene (Ar = EDOT) and 2,3,5,6‐tetrafluoroaniline (Ar = TFANi) were synthesized via polycondensation initiated by ammonium persulfate. The NH₂ group content in the copolymers was determined by analyzing the ¹H NMR spectra of the N‐acetylated copolymers. Copolymers crosslinked by viologen (1,1'‐disubstituted 4,4'‐bipyridinium dichloride) were obtained by reaction involving the reactive NH₂ groups in the copolymers. The absorption wavelengths of solutions of the copolymers and the electrochemical oxidation and reduction potentials of cast films of the copolymers were affected by the electrical properties of the Ar unit. © 2016 Society of Chemical Industry     

A novel resistive‐type humidity sensor based on poly(p‐diethynylbenzene)

Poly(p‐diethynylbenzene) (PDEB) synthesized with nickel catalyst Ni(CC ○ CCH)₂(PPh₃)₂ (Ni C) in dioxane–toluene mixed‐solvent system at 25°C shows a rich trans structure with pendant‐group ( ○ CCH) content of about 35% having higher molecular weight and good solubility. A novel resistive‐type humidity sensor based on PDEB is presented. Its humi‐sensing characteristics are described and discussed. The impedance of the sensor changed from ∼ 10³–10⁷ Ω in almost the whole humidity range [∼ 15–92% relative humidity (RH)], which is low compared with sensors based on other humi‐sensitive conjugate polymers, and hysteresis of no more than 3% RH was observed. The sensor prepared by Langmuir–Blodgett (LB) deposition method shows the best humidity response. An explanation of humi‐sensing behavior of PDEB is attempted by taking into account the interaction between hydrogen protons and super π‐conjugate orbits in PDEB. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2010–2015, 1999     

Rheological and thermal properties of blends of modified poly(ethylene terephthalate) with p‐acetoxybenzoic acid and poly(butylene terephthalate)

Blending of thermotropic liquid crystalline polyesters (LCPs) with conventional polymers could result in materials that can be used as an alternative for short fiber‐reinforced thermoplastic composites, because of their low melt viscosity as well as their inherent high stiffness and strength, high use temperature, and excellent chemical resistance and low coefficient of expansion. In most of the blends was used LCP of 40 mol % of poly(ethylene terephthalate) (PET) and 60 mol % of p‐acetoxybenzoic acid (PABA). In this work, blends of several copolyesters having various PABA compositions from 10 to 70 mol % and poly(butylene terephthalate) (PBT) were prepared and their rheological and thermal properties were investigated. For convenience, the copolyesters were designated as PETA‐x, where x is the mol % of PABA. It was found that PET‐60 and PET‐70 copolyesters decreased the melt viscosity of PBT in the blends and those PBT/PETA‐60 and PBT/PETA‐70 blends showed different melt viscosity behaviors with the change in shear rate, while blends of PBT and PET‐x having less than 50 mol % of PABA exhibited totally different rheological behaviors. The blends of PBT with PETA‐50, PETA‐60, and PETA‐70 showed the morphology of multiple layers of fibers. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1797–1806, 1999     

Biodegradable studies of poly(trimethylenecarbonate‐ε‐caprolactone)‐block‐poly(p‐dioxanone), poly(dioxanone), and poly(glycolide‐ε‐caprolactone) (Monocryl®) monofilaments

The aim of the study was to investigate the mechanical properties and biodegradability of poly(trimethylenecarbonate‐ε‐caprolactone)‐block‐poly(p‐dioxanone) [P(TMC‐ε‐CL)‐block‐PDO] in comparison with poly(p‐dioxanone) and poly(glycolide‐ε‐caprolactone) (Monocryl®) monofilaments in vivo and in vitro. P(TMC‐ε‐CL)‐block‐PDO copolymer and poly(p‐dioxanone) were prepared by using ring‐opening polymerization reaction. The monofilament fibers were obtained using conventional melt spun methods. The physicochemical and mechanical properties, such as viscosity, molecular weight, crystallinity, and knot security, were studied. Tensile strength, breaking strength retention, and surface morphology of P(TMC‐ε‐CL)‐block‐PDO, poly(p‐dioxanone), and Monocryl monofilament fibers were studied by immersion in phosphate‐buffered distilled water (pH 7.2) at 37°C and in vivo. The implantation studies of absorbable suture strands were performed in gluteal muscle of rats. The polymers, P(TMC‐ε‐CL)‐block‐PDO, poly(p‐dioxanone), and Monocryl, were semicrystalline and showed 27, 32, and 34% crystallinity, respectively. Those mechanical properties of P(TMC‐ε‐CL)‐block‐PDO were comparatively lower than other polymers. The biodegradability of poly(dioxanone) homopolymer is much slower compared with that of two copolymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 737–743, 2006     

Preparation,optimization, and voltammetric characteristics of poly(o‐phenylenediamine) film as a dopamine‐selective polymeric membrane

Poly(o‐phenylenediamine) films were electrochemically prepared on gold electrodes from the corresponding monomer in an aqueous solution at a constant potential. The polymeric films prepared in this one‐step procedure were found to be thin and insoluble in the aqueous solution. Cyclic and differential pulse voltammetric techniques were used to examine the permeation properties of ascorbic acid and dopamine at the resultant polymeric film electrode. Then, the effects of the chemical and electrochemical variables (e.g., film thickness, polymerization potential, concentrations of monomer and electrolyte) on the permselectivity characteristics of the polymeric film were systematically investigated and the optimal values for each parameter were determined. Furthermore, it was found that the optimized polymer electrode was found to be stable for the successive runs. As a result, it is claimed that poly(o‐phenylenediamine) film can be used as a dopamine‐selective polymeric membrane. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 327–332, 2001     

Substituent effect on the optoelectronic properties of poly(p‐phenylenevinylene) based conjugated‐nonconjugated copolymers

Two classes of light emitting Poly(p‐phenylenevinylene) (PPV) based conjugated‐nonconjugated copolymers (CNCPs) have been synthesized. The conjugated chromophores containing 2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene (MEHPV) and 2,5‐dimethyl‐1,4‐phenylenevinylene (DMPV) moieties are rigid segments and nonconjugated portion containing hexyl units are flexible in nature. All copolymers were synthesized by well‐known Wittig reaction between the appropriate bisphosphonium salts and the dialdehyde monomers. The resulting polymers were found to be readily soluble in common organic solvents like chloroform, THF and chlorobenzene. The effect of chromophore substituents on the optical and redox properties of the copolymers has been investigated. Color tuning was carried out by varying the molar percentage of the comonomers. The UV‐Vis absorption and PL emission of the copolymers were in the range 314–395 nm and 494–536 nm respectively. All the polymers show good thermal stability. Polymer light‐emitting diodes (PLEDs) were fabricated in ITO/PEDOT:PSS/emitting polymer/cathode configurations of selected polymers using double‐layer, LiF/Al cathode structure. The emission maxima of the polymers were around 499–536 nm, which is a blue‐green part of the color spectrum. The threshold voltages of the EL polymers were in the range of 5.4–6.2 V. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of poly(p‐phenylene)‐graft‐poly(ε‐caprolactone) copolymers by combined ring‐opening polymerization and cross‐coupling processes

2,5‐Dibromo‐1,4‐(dihydroxymethyl)benzene was used as initiator in ring‐opening polymerization of ε‐caprolactone in the presence of stannous octoate (Sn(Oct)₂) catalyst. The resulting poly(ε‐caprolactone) (PCL) macromonomer, with a central 2,5‐dibromo‐1,4‐diphenylene group, was used in combination with 1,4‐dibromo‐2,5‐dimethylbenzene for a Suzuki coupling in the presence of Pd(PPh₃)₄ as catalyst or using the system NiCl₂/bpy/PPh₃/Zn for a Yamamoto‐type polymerization. The poly(p‐phenylenes) (PPP) obtained, with PCL side chains, have solubility properties similar to those of the starting macromonomer, ie soluble in common organic solvents at room temperature. The new polymers were characterized by ¹H and ¹³C NMR and UV spectroscopy and also by GPC measurements. The thermal behaviour of the precursor PCL macromonomer and the final poly(p‐phenylene)‐graft‐poly(ε‐caprolactone) copolymers were investigated by thermogravimetric analysis and differential scanning calorimetry analyses and compared. Copyright © 2004 Society of Chemical Industry     

Kinetics of thermal degradation of poly(p‐phenylene benzobisoxazole)

The kinetics of thermal degradation of poly (p-phenylen benzobisoxazole) (PBO) were studied by thermogravimetric analysis (TG) in dynamic nitrogen gas at four different heating rates: 5, 10, 15, 20°C/min. The activation energy calculated by Kissinger Method was 352.19 kJ/mol, and the mean value of activation energies evaluated by Flynn-Wall-Ozawa Method was 338.32 kJ/mol. The degradation kinetic model of PBO followed the mechanism of random scission of weak bonds of PBO molecule and impact of the active groups obtained from the broken bonds, Mampel Power equation with integral form G(α) = α^3/2 and differential form . And the mathematical equation of kinetic compensation effect was ln A = 0.1365 E_a − 1.4102. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3675–3679, 2007     

Mechanism of degradation of poly(p‐phenylene benzobisoxazole) under hydrolytic conditions

Poly(p‐phenylene benzobisoxazole) (PBO) fiber has received great interest because of its excellent mechanical properties and good thermal stability. The objective of this study was to expose degradation mechanism of PBO under neutral and acidic conditions by molecular mass and Fourier transform infrared (FTIR) spectroscopy. Results were not consistent with the classic degradation mechanism, which indicates that degradation should occur through the ring opening and chain scission of the benzoxazole ring. The FTIR absorption spectra of PBO suggested that the o‐hydroxy amide linkage (the open ring structure) was present in the PBO molecule chain to some extent because of the incomplete polymerization. Further investigation showed that hydrolysis might occur in the open ring section during hydrolytic degradation. Based on the experimental data, a new degradation mechanism was proposed. It suggests that, in the early and middle stages, hydrolysis occurred primarily in the o‐hydroxy amide linkage of the open ring. The concentration of the o‐hydroxy amide structure determined the speed of degradation of PBO. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011