Studies on the oxidation of phenols catalyzed by a copper(II)–Schiff base complex in aqueous solution under mild conditions

The catalytic oxidation of phenol with hydrogen peroxide using a synthetic copper(II)–Schiff base complex as catalyst has been investigated in phosphate buffer at pH 7 and 25 °C. In order to further investigate the reaction pathway, the catalytic oxidation of hydroquinone, p‐benzoquinone and catechol were also studied under the same conditions. These reactions were found to be pseudo‐first‐order with respect to the concentration of phenolic substances. The rate constants were also calculated. In the presence of catalyst, the kinetics and the HPLC analysis showed that for the first step phenol was oxidized to hydroquinone and catechol, and the catalyst easily promoted the formation of hydroquinone but not catechol, for the second step the dihydroxybenzenes were further oxidized to benzoquinone, and lastly short‐chain acids, including maleic acid and oxalic acid, were formed. The activity of the catalyst hardly decreased during the whole reaction. Addition of imidazole accelerated the oxidation of phenol. The catalytic decomposition of hydrogen peroxide using this catalyst was also investigated. Copyright © 2005 Society of Chemical Industry     

A novel silk fibroin‐supported iron catalyst for hydroxylation of phenol

The aim of this study was to explore the potential use of silk fibroin (SF) as a catalyst support material for phenol hydroxylation reactions. Iron‐substituted silk fibroin fibers were prepared using formic acid at room temperature and characterized using inductively coupled plasma atomic‐emission spectrometry, scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR) and optical microscopy. Measurement of an FTIR spectrum showed that the secondary structure was β‐structure before and after iron substitution. To evaluate the catalytic properties of prepared catalyst, phenol hydroxylation reaction was carried out using aqueous hydrogen peroxide as an oxidant. An excellent transformation of phenol into dihydroxybenzenes (catechol and hydroquinone) was achieved. Phenol conversions of 3.3%, 61.2%, and 80.3% were obtained at room temperature, 40 °C and 60 °C respectively. It was found that no further phenol conversion proceeded because catalysts became separated from the reaction system during the reaction. No significant leaching of the iron was detected. Catalyst could be reused several times without a significant change in activity. Parent silk fibroin fibers without iron were inactive. Copyright © 2006 Society of Chemical Industry     

Preparation of nanometer‐sized poly(methacrylic acid) particles in water‐in‐oil microemulsions

A water‐in‐oil microemulsion, water‐in‐cyclohexane stabilized by poly(ethylene glycol) tert‐octylphenyl, was developed to prepare poly(methacrylic acid) (PMAA) particles. Up to 100% conversion of the amphiphilic monomer, methacrylic acid (MAA), which could not be converted to the polymer efficiently in a dioctylsulfosuccinate sodium salt/toluene microemulsion, was achieved. The viscosity‐average molecular weight of the PMAA prepared was 1.45 × 10⁵ g/mol. The effects of some polymerization parameters, including the reaction temperature and the concentrations of the initiator and the monomer, on the polymerization of MAA were investigated. The results showed that the polymerization rate of MAA was slower than that of acrylamide in the microemulsions reported in the literature. The degree of conversion increased with the initiator concentration, reaction temperature, and monomer concentration. However, the stable microemulsions became turbid during the polymerization when the reaction temperature was at 70°C or at a high monomer concentration (40 wt %) The synthesized PMAA particles were spherical and had diameters in the range of ～50 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2497–2503, 2006     

pH electrodes constructed from polyaniline/zeolite and polypyrrole/zeolite conductive blends

A new type of solid state electrodes sensitive to pH changes is described, in which the chemical‐sensitive layer consists of Pt microparticles deposited on a conducting polymer (polyaniline, polypyrrole) blend containing 22.7% w/w zeolite. These sensors are stable in aqueous electrolyte solutions of low pH value at temperatures up to 45°C with response time in seconds. At 25°C, sensor sensitivity was ?310 ± 40 mV/pH and ?1300 ± 100 mV/pH for polyaniline and polypyrrole blends, respectively. Interferences appear to be acceptably small. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1853–1856, 2006     

Synthesis and properties of poly ether nitrile sulfone copolymers with pendant methyl groups

Poly ether nitrile and poly ether nitrile sulfone copolymers with pendant methyl groups were prepared by the nucleophilic substitution reaction of 2,6′‐dichlorobenzonitrile with methyl hydroquinone and with varying mole proportions of methyl hydroquinone and 4,4′dihydroxydiphenylsulfone using N‐methyl pyrrolidone as solvent in the presence of anhydrous K₂CO₃. The polymers were characterized by different physicochemical techniques. Copolymer composition was determined using FTIR technique. Thermogravimetric data reveals that all the polymers were stable up to 420°C with a char yield above 40% at 900°C in N₂ atmosphere. The glass transition temperature was found to increase and the activation energy and inherent viscosities were found to decrease with increase in concentration of the 4,4′‐dihydroxydiphenylsulfone units in the polymer. Trimerization reactions are found to be favorable with increase in concentration of methyl hydroquinone units in the polymer. Crystallinity of the polymer was also studied using wide angle X‐ray diffraction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1303–1309, 2006     

Oxidation of phenol by aqueous hydrogen peroxide catalysed by ferric ion-catechol complexes

Phenol has been oxidised with aqueous hydrogen peroxide under a wide variety of conditions and yields of the catechol and hydroquinone products recorded. Catalysts tested included a number of transition metal and related ions of which only Cu⁺, Cu²⁺, Cr³⁺, WO₄^2-, Hg²⁺, Fe²⁺, and Fe³⁺ gave any degree of success. Extensive tests with ferric ion established 2.5:1000, Fe³⁺:phenol mole ratio as being the optimum catalytic range. Temperatures lower than 30°C gave relatively high catechol:hydroquinone product ratios, about 1.9:1, but lowered the yields of dihydroxybenzenes to about 70% of theory. From experiments conducted over the pH range of 1 to 8 the optimum pH for high yield reactions was found to be 2 to 3. Operating at a hydrogen peroxide:phenol mole ratio of 0.30:1.0 gave the highest catechol:hydroquinone product ratios, 1.6:1.0. The catechol:hydroquinone ratio produced decreased as the ratio of reacting peroxide to phenol was increased. Optimised conditions gave dihydroxybenzene yields of 84 and 53% on phenol and hydrogen peroxide respectively, and ratios of 1.5:1 and 2.0:1, catechol:hydroquinone. A research stage economic summary from averaged pairs of experimental results gave a value added of $3.19 (technical grade products) or $8.47 (pure grades) per kg of catechol on a raw material cost base of $2.87, as two among four calculated cost evaluation scenarios.     

Modification of high‐performance polymer composite through high‐energy radiation and low‐pressure plasma for aerospace and space applications

In this investigation, attempts are made to modify a high‐performance polymer such as polybenzimidazole (PBI) (service temperature ranges from ?260°C to +400°C) through high‐energy radiation and low‐pressure plasma to prepare composite with the same polymer. The PBI composites are prepared using an ultrahigh temperature resistant epoxy adhesive to join the two polymer sheets. The service temperature of this adhesive ranges from ?260°C to +370°C, and in addition, this adhesive has excellent resistance to most acids, alkalis, solvents, corrosive agents, radiation, and fire, making it extremely useful for aerospace and space applications. Prior to preparing the composite, the surface of the PBI is ultrasonically cleaned by acetone followed by its modification through high‐energy radiation for 6 h in the pool of a SLOWPOKE‐2 (safe low power critical experiment) nuclear reactor, which produces a mixed field of thermal and epithermal neutrons, energetic electrons, and protons, and γ‐rays, with a dose rate of 37 kGy/h and low‐pressure plasma through 13.56 MHz RF glow discharge for 120 s at 100 W of power using nitrogen as process gas, to essentially increase the surface energy of the polymer, leading to substantial improvement of its adhesion characteristics. Prior to joining, the polymer surfaces are characterized by estimating surface energy and electron spectroscopy for chemical analysis (ESCA). To determine the joint strength, tensile lap shear tests are performed according to ASTM D 5868–95 standard. Another set of experiments is carried out by exposing the low‐pressure plasma‐modified polymer joint under the SLOWPOKE‐2 nuclear for 6 h. Considerable increase in the joint strength is observed, when the polymer surface is modified by either high‐energy radiation or low‐pressure plasma. There is further significant increase in joint strength, when the polymer surface is first modified by low‐pressure plasma followed by exposing the joint under high‐energy radiation. To simulate with spatial conditions, the joints are exposed to cryogenic (?196°C) and high temperatures (+300°C) for 100 h. Then, tensile lap shear tests are carried out to determine the effects of these environments on the joint strength. It is observed that when these polymeric joints are exposed to these climatic conditions, the joints could retain their strength of about 95% of that of joints tested under ambient conditions. Finally, to understand the behavior of ultrahigh temperature resistant epoxy adhesive bonding of PBI, the fractured surfaces of the joints are examined by scanning electron microscope. It is observed that there is considerable interfacial failure in the case of unmodified polymer‐to‐polymer joint whereas surface‐modified polymer essentially fails cohesively within the adhesive. Therefore, this high‐performance polymer composite could be highly useful for structural applications in space and aerospace. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1959–1967, 2006     

Synthesis and characterization of cholesteric thermotropic liquid crystalline polyesters

Cholesteric liquid crystalline polyesters were successfully synthesized from isosorbide, methyl hydroquinone, and isophthaloyl chloride. Homo/copolyesters were synthesized by the solution polycondensation method, for which a mild organic base such as pyridine was employed. Inherent viscosities of polyesters P‐3–P‐5 were in the range of 0.31–0.39 dL/g at 25°C in chloroform, and polyesters P‐1 and P‐2 were insoluble in chloroform. Homo/copolyesters based on isosorbide, methyl hydroquinone, and isophthalic acid had thermal stability at more than 300°C on the basis of 10% weight loss. The thermotropic liquid crystalline properties were examined by differential scanning calorimetry and polarizing optical microscopy. Wide‐angle X‐ray diffraction study demonstrated that polyesters P‐1, P‐2, and P‐3 were semicrystalline, whereas the degree of crystallinity of polyesters P‐4 and P‐5 was less than 5%. Copolyester P‐4 showed formation of a yellow iridescent streak at 209°C on heating and development of a Grandjean texture at 270°C on heating. These are typical textures of the cholesteric liquid crystalline phase. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1232–1237, 2007     

Effect of phenol derivatives on molecular dimensions of poly(N‐vinyl‐2‐pyrrolidone) in aqueous solution

The unperturbed dimensions and thermodynamic parameters of poly(N‐vinyl‐2‐pyrrolidone) (PVP) were studied in aqueous solutions in the presence of certain phenolic cosolutes (phenol, catechol, hydroquinone, resorcinol, and phloroglucinol). The intrinsic viscosities at 25°C and the θ temperature, linear and thermodynamic expansions, and root mean square end to end distances were evaluated for the system that was employed. The sequence was obtained due to the effectiveness of the cosolutes in the order of phloroglucinol > resorcinol > hydroquinone > catechol > phenol. The effects of these cosolutes on the main thermodynamic parameters were reported to be due to the number and position of hydroxyl groups present. The thermodynamic interaction parameter was also evaluated and the enthalpic and entropic contributions were verified. The condition required for the θ temperature to correspond to a Flory interaction parameter of 0.5 was well provided, yielding a θ temperature of almost 0.5 for the system under study. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 473–477, 2002; DOI 10.1002/app.10047     

Processing robustness for a phenylethynyl‐terminated polyimide composite

The processability of a phenylethynyl‐terminated imide resin matrix (PETI‐5) composite was investigated. Unidirectional prepregs were made through the coating of an N‐methylpyrrolidone solution of an amide acid oligomer (PETAA‐5/NMP) onto unsized IM7 fibers. Two batches of prepregs were used: one was made by the National Aeronautics and Space Administration in house, and the other was from an industrial source. The composite processing robustness was investigated with respect to the prepreg shelf life, the effect of B‐staging conditions, and the optimal processing window. The prepreg rheology and open hole compression (OHC) strengths were not to affected by prolonged ambient storage (i.e., up to 60 days). Rheological measurements indicated that the PETAA‐5/NMP processability was only slightly affected over a wide range of B‐stage temperatures (from 250 to 300°C). The OHC strength values were statistically indistinguishable among laminates consolidated under various B‐staging conditions. An optimal processing window was established with response surface methodology. The IM7/PETAA‐5/NMP prepreg was more sensitive to the consolidation temperature than to the pressure. A good consolidation was achievable at 371°C (700°F)/100 psi, which yielded a room‐temperature OHC strength of 62 ksi. However, the processability declined dramatically at temperatures below 350°C (662°F), as evidenced by the OHC strength values. The processability of the IM7/PETI‐5 prepreg was robust. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3212–3221, 2006     

Structural modification and characterization of lignosulfonate by a reaction in an alkaline medium for its incorporation into phenolic resins

We studied the enhancement of lignin reactivity in an alkaline medium, using sodium hydroxide in a microreactor set. The chemical composition and structural characterization of the reacted lignosulfonate in terms of the phenolic hydroxyl groups, aromatic protons, weight‐average molecular weight, number‐average molecular weight, and lignosulfonate content of all reacted lignins were determined. The techniques that we used were ultraviolet spectroscopy, proton nuclear magnetic resonance spectroscopy, and aqueous gel permeation chromatography. Using response surface methodology, we studied how the temperature and reaction time affected the lignin properties. The reaction conditions were temperatures between 116 and 180°C and reaction times between 18 and 103 min. Modeled response surfaces showed that the two factors affected the lignin properties within the studied ranges. The phenolic hydroxyl groups, aro matic protons, and lignosulfonate content increased when the severity of the treatment increased. The weight‐average molecular weight, number‐average molecular weight, and solid yield (%) decreased when the severity of the treatment increased. The reactivity of the modified lignins was studied with a formaldehyde reactivity test: more severe conditions produced greater improvements in the formaldehyde reactivity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3286–3292, 2006     

Synthesis and characterization of an interpenetrating polymer network composed of poly(methacrylic acid) and poly(vinyl alcohol)

Temperature and pH‐responsive interpenetrating polymer network (IPN) hydrogels, constructed with poly(methacrylic acid) (PMAA) and poly(vinyl alcohol) (PVA), by a sequential IPN method, were studied. The characterization of IPN hydrogels was investigated by Fourier‐transform infrared spectroscopy, differential scanning calorimetry (DSC) and swelling under various conditions. The IPN hydrogels exhibited relatively high swelling ratios, in the range 230–380 %, at 25 °C. The swelling ratios of the PMAA/PVA IPN hydrogels were pH and temperature dependent. DSC was used for the quantitative determination of the amounts of freezing and non‐freezing water. The amount of free water increased with increasing PMAA content in the IPN hydrogels. Copyright © 2004 Society of Chemical Industry     

Preparation and cytocompatibility of chitosan‐modified polylactide

Chitosan‐modified PLA (CMPLA) was fabricated to improve cytocompatibility of polylactide (PLA). PMAA‐grafted PLA (PMAA‐PLA) was obtained through α‐methacrylic acid (MAA) grafted polymerization on PLA surface with photooxidization and UV irradiation. Steady PMAA‐PLA microparticle suspension with an average size as 172.8 ± 3.6 nm and zeta potential as ?95.0 ± 0.6 mV was prepared through solvent volatilization. By static electricity interaction and other interactions between PMAA‐PLA microsparticles and chitosan molecules, CMPLA was obtained. FTIR, XPS, SEM, and zeta potential analyses indicated that CMPLA was modified with chitosan molecules uniformly. Compared with the PLA control, CMPLA adapted to supporting the attachment and proliferation of L929 cells better. The obtained CMPLA was expected to be used as perfect biomaterial for tissue regeneration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and pH‐responsive performance of silane‐modified poly(methylacrylic acid)

The poly(methylacrylic acid) modified by silane [poly(methylacrylic acid‐co‐vinyl triethoxylsilane) (PMAA)] was prepared via free‐radical polymerization with different mass ratios of methylacrylic acid to vinyl triethoxylsilane (VTES). The swelling performance of the prepared PMAA in different solutions with various pH values, salt species (NaCl and CaCl₂), and concentrations was investigated in detail. The results indicated that the introduction of silane boosted the stability of the obtained PMAA in aqueous solutions in the presence of an increased quantity of VTES additive. Meanwhile, the different swelling ratios of PMAA in various pH solutions showed a high pH responsivity. In addition, we found that when the PMAA underwent a number of swelling–deswelling cycles, it demonstrated the good reversibility properties when the pH value of the swelling medium was changed from 9.0 to 1.4. Moreover, the swelling mechanism of PMAA in different solutions with different pH values was investigated. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40403.     

Structure and applications of CB/crystal fluoride resin alloy in self‐regulated heating cables

A conductive composite was prepared by blending carbon black with a modified crystal fluoride resin alloy. The formulation and the processing technology were optimized, and the positive‐temperature‐coefficient (PTC) characteristics under different conditions were studied by SEM, WAXD, and DSC. Relationships between the properties and the structures are illustrated, and applications of this composite in high‐grade temperature self‐regulating heating cables (135°C) are suggested. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2664–2669, 2003     

Cyanuric acid–epichlorohydrin prepolymers

In this study, we investigated the reaction of cyanuric acid and epichlorohydrin (ECH). SnCl₄ was used as a catalyst. Several reaction conditions were tested, and the products were analyzed by means of Fourier transform infrared and ¹H‐NMR spectroscopy, hydroxyl group content, molar mass, elemental and thermal analysis, viscosity, and density. ECH reacted with the amine groups of the cyanuric acid ring to form lateral chains that contained chloroalkyl and hydroxyl end groups. Full substitution of the amine groups was observed in all of the synthesized products. The solvent used in the synthesis was found to be very important for the structure of the final prepolymers. When N,N‐dimethylformamide was used, relatively low‐molar‐mass prepolymers of cyanuric acid and ECH were obtained. When solvents with low dielectric constants were used, no reaction with cyanuric acid was observed. The prepared prepolymers were thermally stable up to 160°C. At this temperature, degradation started via the lateral chains. The viscosity of the products decreased as the ECH–cyanuric acid ratio increased, whereas the density remained basically constant. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3684–3691, 2006     

Oxidation of hydroquinone to p‐benzoquinone catalyzed by Cu(II) supported on chitosan flakes

Copper (sorbed on chitosan flakes) was used as a catalyst for the oxidation of hydroquinone, with dioxygen (from air) and hydrogen peroxide as oxidizing agents. The supported catalyst was very efficient at oxidizing hydroquinone into p‐benzoquinone. With hydrogen peroxide at pH 5.8, drastic oxidizing conditions led to the formation of subproducts. With a short contact time, together with the use of a low hydrogen peroxide concentration and a small amount of the catalyst, the formation of subproducts could be minimized. The influence of the catalyst/substrate and hydrogen peroxide/substrate ratios was investigated to determine optimum experimental conditions for a high initial oxidation rate and a high production of p‐benzoquinone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3034–3043, 2006     

Simultaneous determination of hydroquinone and catechol using poly(p‐aminobenzoic acid) modified glassy carbon electrode

The electrochemical redox reaction of hydroquinone (HQ) and catechol (CC)was investigated with poly‐(p‐aminobenzoic acid) modified glassy‐carbon electrode (poly‐p‐ABA/GCE) via cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The poly‐p‐ABA/GCE has shown an excellent electrocatalytic activity for HQ and CC in 0.1 mol L^?1 phosphate buffer solution (PBS). The oxidation and reduction separation (ΔE) has been decreased from 353 to 32 mV for HQ and from 228 to 33 mV vs. SCE for CC at the bare GCE and poly‐p‐ABA/GCE respectively. DPV curves show that the oxidation potential of HQ and CC has a separation about 105 mV at the poly‐p‐ABA/GCE. Moreover, the oxidation current of HQ and CC has been enhanced two and four times respectively at the modified electrode. Using DPV method, a highly selective and simultaneous determination of HQ and CC has been explored at the poly‐p‐ABA/GCE. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of composition of hardener on the curing and aging for an epoxy resin system

Different mixture ratios of Shell Epon 828 (based on diglycidyl ether of bisphenol A, DGEBA) and Shell EPI‐CURE 3046 (based on triethylenetetramine, TETA) were evaluated under different environments of isothermal curing at 80°C in DSC, room temperature curing in air, and aging in water at 45°C. The curing reactions were monitored using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and infrared spectroscopy (IR). It was shown that the initial curing rate increased with the amount of hardener. However, the epoxy groups in samples with excess hardener were prone to reaction with primary amines located at the ends of TETA molecules, resulting in a less dense epoxy network. During aging in water at 45°C, significant effects of water on the postcure and the increased water absorption with an increase of hardener amount were observed. The DMA results show that the samples with hardener around stoichiometric composition have the greatest storage modulus while curing in air environment. However, the samples with hardener much less than stoichiometric composition have greater storage modulus under aging in water at 45°C. in water at 45°C. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 580–588, 2006     

New soluble cyano‐containing poly(arylene ether) copolymers bearing pendant xanthene groups

Homopolymers and copolymers of poly(arylene ether nitrile) (PAEN)‐bearing pendant xanthene groups were prepared by the nucleophilic substitution reaction of 2,6‐difluorobenzonitrile with 9,9‐bis(4‐hydroxyphenyl)xanthene (BHPX) and with various molar proportions of BHPX to hydroquinone (100/0 to 40/60) with N‐methyl‐2‐pyrrolidone (NMP) as a solvent in the presence of anhydrous potassium carbonate. These polymers had inherent viscosities between 0.61 and 1.08 dL/g, and their weight‐average molecular weights and number‐average molecular weights were in the ranges 34,200–40,800 and 17,800–20,200, respectively. All of the PAENs were amorphous and were soluble in dipolar aprotic solvents, including NMP, N,N‐dimethylformamide, and N,N‐dimethylacetamide and even in tetrahydrofuran and chloroform at room temperature. The resulting polymers showed glass‐transition temperatures (T_g's) between 220 and 257°C, and the T_g values of the copolymers were found to increase with increasing BHPX unit content in the polymer. Thermogravimetric studies showed that all of the polymers were stable up to 422°C with 10% weight loss temperatures ranging from 467 to 483°C and char yields of 54–64% at 700°C in nitrogen. All of the new PAENs could be cast into transparent, strong, and flexible films with tensile strengths of 106–123 MPa, elongations at break of 13–17%, and tensile moduli of 3.2–3.7 GPa. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011