Polymer precursor to diamondlike carbon prepared by the polymerization of α,α,α‐trichlorotoluene and acetonitrile

A novel liquid/solid two‐phase reaction of α,α,α‐trichlorotoluene (PhCCl₃) and acetonitrile (AN) has been discovered that produces a carbon‐based polymer with diamondlike structure at the atomic level. The solid phase is potassium hydroxide particles, and the liquid phase is a tetrahydrofuran solution of PhCCl₃ and AN containing a certain amount of tetrabutylammonium bromide as a phase‐transfer catalyst. The structure of the carbon‐based polymer has been characterized by elemental analysis, Fourier transform infrared spectroscopy, and ¹H‐ and ¹³C‐NMR spectroscopy. The pyrolysis of the carbon‐based polymer at 800°C under a nitrogen atmosphere leads to the formation of a diamondlike carbonaceous material according to the results of X‐ray photoelectron spectroscopy and Raman spectroscopy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 16–23, 2003     

Thermal degradation kinetics of isotactic and atactic polypropylene

The thermal degradation of isotactic and atactic polypropylene was investigated in bulk and in solution. The degradation in bulk was studied with thermogravimetric analysis, and the degradation in solution was studied by the dissolution of the polymer in paraffin oil. The degradation in solution was investigated from 230 to 350°C. The effect of the hydrogen donor on the degradation of the polymer in solution was also studied at 350°C. Continuous distribution kinetics were employed to model the degradation kinetics for the degradation in solution. The rate coefficients were obtained, and the activation energy was calculated from an Arrhenius plot. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2206–2213, 2003     

Surface modification of polybutadiene facilitated by supercritical carbon dioxide

The hydrophilicity of polymers can be improved through surface modification, traditionally done with conventional organic solvents, but these may cause the deterioration of polymer bulk properties due to irreversible polymer swelling. However, supercritical carbon dioxide (scCO₂) not only swells the polymer reversibly, but also acts as a convenient transport medium for monomeric solutes, which may be subsequently polymerized. Thus we are able to modify the polymer surface without affecting its bulk strength and durability. Here we report scCO₂ surface modification of polybutadiene using ultraviolet‐visible (UV/Vis) and Fourier transform infrared (FTIR) spectroscopy. Monomers such as 3‐vinylbenzoic acid and crotonic acid are used to study the effects of pressure, solute structure, and reaction mechanism on the diffusion rates and partitioning of monomers between the fluid phase and the polymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 522–530, 2003     

Conducting blends of poly(o‐toluidine) and ethylene–propylene–diene terpolymer

Poly(o‐toluidine) (POT) is an electroactive polymer with poor mechanical and thermal characteristics. We examined the scope for improving such properties by making blends of POT with ethylene–propylene–diene rubber (EPDM). We prepared POT–EPDM blends containing different weight fractions of POT by intimately mixing known volumes of separate solutions of the two polymers (POT in THF and EPDM in toluene). Films of EPDM and POT–EPDM blends in solution were obtained by spreading, solvent evaporation, and film casting techniques. POT, EPDM, and their blends were characterized in solution by ultraviolet‐visible spectroscopy, and the respective dried samples were analyzed by Fourier transform infrared spectroscopy and thermogravimetry. The polymer samples were further analyzed morphologically by scanning electron microscopy, and their tensile strengths were also evaluated. Spectroscopic and thermal studies of the blends indicated some sort of interaction between the two constituent polymers. The direct current electrical conductivity of the blends in increasing order of POT loading (12.5–100%) was in the range 9.9 × 10^?5 to 11.6 × 10^?2 S cm^?1. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2550–2555, 2003     

Synthesis and properties of hydrophilic polymers. IX. Synthesis,biodegradability, and metal complexation of copolymers of ethylenediaminetetraacetic acid dianhydride and lactose

The synthesis and characterization of poly(ethylenediaminetetraacetic acid‐co‐lactose) with pendant carboxylic groups of high molar mass (132 kg mol^?1) is described. The polycondensate was hydrolytically and microbiologically degradable with conventional microbiological methods. The metal‐complexing properties of the polyester were studied for Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Sr(II), Cd(II), Pb(II), and Al(III) ions in aqueous solution with the liquid‐phase polymer‐based retention (LPR) method. In addition, the complexing capacity of the Cu(II)‐saturated copolymer was determined by thermogravimetric analysis to be 182 mg g^?1 of polymer. According to the retention profiles determined as a function of the filtration factor with LPR in conjunction with inductively coupled plasma spectrometry, Cr(III) and Fe(III) showed a strong interaction with this polymer under these conditions, as indicated by retention values of about 100% at pH 5. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 650–657, 2003     

Synthesis and characterization of novel crosslinked polyurethane–acrylate electrolyte

Flexible, transparent, and crosslinked polymer films were synthesized by polymerization of PEG‐modified urethane acrylate using a simple method. A series of novel solid polymer electrolytes and gel electrolytes were prepared based on this type of polymer film. To understand the interactions among salt, solvent, and polymer, the swelling behaviors of the crosslinked polymer in pure propylene carbonate (PC) and liquid electrolyte solutions (LiClO₄/PC) were investigated. The results showed that the swelling rate in the electrolyte solution containing moderate LiClO₄ was greater than that in pure PC. Thermogravimetric analysis (TGA) also supported the interaction between the solvent and polymer. The morphology and crystallinity of the crosslinked polymer and polymer electrolytes were studied using atomic force microscopy (AFM) and wide‐angle X‐ray diffraction (WAXD) spectroscopy. The effects of the content of the electrolyte solution on the ionic conductivity of gel electrolytes were explored. The dependence of the conductivity on the amount of the electrolyte solution was nonlinear. With a different content of the plasticizer, the ionic conduction pathway of the polymer electrolytes would be changed. The best ionic conductivity of the gel electrolytes, which should have good mechanical properties, was 4 × 10^r?3 S cm^?1 at 25°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 340–348, 2003     

Poly(acrylic acid‐co‐vinylsulfonic acid): Synthesis,characterization, and properties as polychelatogen

The synthesis of the water‐soluble poly(acrylic acid‐co‐vinylsulfonic acid) at different feed monomer ratios, while maintaining constant the total number of mol, was carried out by radical polymerization. The copolymers were characterized by FTIR and ¹H‐NMR spectroscopies. The copolymer composition was determined by its sulfur content and by potentiometric titration. The metal ion binding properties for Ni(II) and Cu(II) in the aqueous phase were studied using the liquid‐phase polymer‐based retention (LPR) technique for two values of ionic strength. For comparison, the retention properties of both homopolymers were included. The complexing ability of the polymer was determined by the relative amount of carboxylic acid groups. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1698–1704, 2003     

Mechanism of persulfate decomposition in aqueous solution at 50°C in the presence of vinyl acetate and nitrogen

The rate of the thermal decomposition of potassium persulfate has been studied in an unbuffered aqueous solution at 50°C in nitrogen atmosphere in the presence of vinyl acetate (VA) monomer (M). It has been found that the initial rate of persulfate decomposition may be written as in the concentration range of persulfate (1.85 × 10^?2–1.85 × 10^?3 m/dm³) and VA (0.054–0.27 m/dm³). The pH of the aqueous solution of persulfate was found to decrease continuously at 50°C, but there was no measurable change of pH of the aqueous solution containing persulfate and VA at 50°C in the presence of nitrogen at the early stages of the reaction. VA, methyl acetate, and ethyl acetate have been found to undergo very slow hydrolysis in aqueous solution at 50°C. The partition coefficient (β) of the monomer between the polymer phase and the aqueous phase was found to be 21 ± 2 in the presence and absence of electrolytes (K₂SO₄, 10^?4–10^?3 m/dm³) by the bromometric estimation of the monomer present in the aqueous phase containing known amounts of monomer [1.80–2.20%, w/v] and freshly prepared polymer (0.3–0.5 g/100 mL). Above 10^?2 (m/dm³) persulfate, the polymer obtained was found to be insoluble in common solvents, viz., acetone, benzene, etc. Highly purified sodium dodecyl sulfate (0.5–5.0 × 10^?3 m/dm³) had no measurable effect on the rate of persulfate decomposition.     

Polymer‐supported palladium(II) complexes and their catalytic study

Chloromethylated poly(styrene–divinylbenzene) copolymers with 8 and 14% crosslinking was functionalized to a Schiff‐base‐bearing polymer by the sequential oxidation of the chloromethyl group to an aldehydic group and subsequent condensation with a base. The anchoring of the metal ion to the liganded polymer beads was carried out by its reaction with an ethanolic solution of palladium(II) chloride. The physicochemical properties of the supported catalyst, including surface area, bulk density, and the swelling of the polymer in polar and nonpolar solvents, were studied. The catalysts were characterized by various techniques, including elemental analysis, DTA–thermogravimetric analysis, Fourier transform infrared spectroscopy, and diffuse reflectance spectroscopy. The surface morphology of the catalyst was studied by scanning electron microscopy. The catalytic hydrogenation of cis‐cyclooctene was investigated with the immobilized catalysts. The effects of various reaction parameters, including catalyst concentration, temperature, and hydrogen pressure on the reduction of olefin, were studied. The rate of the reaction was determined from hydrogen uptake measurements. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 370–378, 2003     

Third‐order nonlinear optical properties of polyureas and polyimide synthesized by microwave irradiation

Polymerization of benzoguanamine (BGA) and 2,4‐tolylenediisocyanate (TDI), BGA–TDI polycondensation polyurea (PU), and pyromellitic dianhydride (PMDA) in solid phase under microwave radiation was studied. In the system of TDI and BGA, the effect of microwave radiation time, the composition and concentration of monomer, the temperature, and the concentration of catalyst on the third‐order optical nonlinearities of polymer were discussed. In the system of PU and PMDA, the effect of imidization degree on third‐order optical nonlinearities was also discussed. The results showed that the prepared polymer had high third‐order nonlinear optical coefficients (PU: χ⁽³⁾ = 1.174 × 10^?13 esu) and fast time responses (24 ps); simultaneously, the third‐order optical nonlinearities of polymer were improved greatly by microwave radiation. The results also showed that third‐order optical nonlinearities were affected not only by the length of the polycondensate chain but also by the molecular structure, which was explained and confirmed by the computation of the AM1 semiempirical method and UV‐visible absorption spectrum. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2611–2617, 2003     

PEEKWC ultrafiltration hollow‐fiber membranes: Preparation,morphology, and transport properties

A series of hollow‐fiber membranes was produced by the dry–wet spinning method from PEEKWC, a modified poly(ether ether ketone) with good mechanical, thermal, and chemical resistance. The fibers were prepared under different spinning conditions, varying the following spinning parameters: polymer concentration in the spinning solution, height of the air gap, and bore fluid composition. The effect of these parameters on the water permeability, the rejection of macromolecules (using dextrane with an average molecular weight of 68,800 g/mol), and the morphology of the membranes was studied. The results were also correlated to the viscosity of the spinning solution and to the ternary polymer/solvent/nonsolvent phase diagram. The morphology of the cross section and internal and external surfaces of the hollow fibers were analyzed using scanning electron microscopy (SEM). All membranes were shown to have a fingerlike void structure and a skin layer, depending on the spinning conditions, varying from (apparently) dense to porous. Pore size measurements by the bubble‐point method showed maximum pore sizes ranging from 0.3 to 2 μm. Permeability varied from 300 to 1000 L/(h^?1 m^?2 bar) and rejection to the dextrane from 10 to 78%. The viscosity of polymer solutions was in the range of 0.2 to 3.5 Pa s. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 841–853, 2004     

Preparation and evaluation of a nanocomposite of polythiophene with Al2O3

The polymerization of thiophene (TP), in bulk and in solution in CHCl₃ by FeCl₃ resulted in the formation of a polymer which was characterized by FTIR as polythiophene (PTP). High yield was realized in the latter case. The polymerization of TP with FeCl₃ and nanodimensional Al₂O₃ resulted in the formation of a nanocomposite which was partly dispersible in aqueous and non‐aqueous media. The dispersibility appeared to be higher when the polymerization was conducted in a suspension containing a higher amount of Al₂O₃. Scanning electron micrographs showed globular particles and the presence of clusters of composite particles. Transmission electron micrographic (TEM) analyses revealed the particle size of the composite to be in the range 22–74 nm. Thermal analyses (TG/DTA) revealed the outstanding stability of PTP–Al₂O₃ composites compared to that of PTP. The conductivity of PTP and of PTP–Al₂O₃ composite was of the order of 10^?3 S cm^?1 for samples doped with I₂. © 2003 Society of Chemical Industry     

Effect of Processing Parameters and Vibrating Field on Poly(Vinyl Chloride) Microcellular Foam Morphology

The effects of processing parameters such as processing pressure, temperature, mixing time and rotor speed on polyvinyl chloride foams were investigated by using a novel microcellular foaming setup. The experimental results show that a proper temperature and a high pressure can promote CO₂ dissolving in polymer, which makes cell density increase and cell size decrease. Increasing mixing time and rotor speed also promote CO₂ dissolving in PVC and speed up forming single-phase polymer/CO₂ solution. The effects of oscillatory shear on polyvinyl chloride cell morphology were also studied. The combined shear improves the mixing, and thus shortens the time needed for homogeneous polymer/supercritical CO₂ solution formation. Foamed samples with the cell density of 1.0 × 10⁷–3.5 × 10⁸ cells/cm³, average cell size of 15–60 µm and bulk density of 0.6–0.87 g/cm³ had been produced.     

Radiation-induced polymerization of ethylene in a pilot plant. I. Bulk process

Radiation-induced bulk polymerization of ethylene was carried out with use of a pilot plant with a 10 liter reactor at pressures of 225–400 kg/cm², temperatures of 30–95°C, ethylene feed rates of 5–28 kg/hr, and dose rate of 3.8 × 10⁵ rad/hr. Characteristics of the process are mild polymerization conditions and capability of producing medium density polyethylene in powder form. The spacetime yield and molecular weight of polymer were in the range of 3.5 to 13.1 g/liter hr and 2.2 × 10⁴ to 14 × 10⁴, respectively. The space-time yield increased with mean residence time and 2.4 powders of pressure, and decreased with temperature. Molecular weight changed similarly with the reaction conditions. These results were consistent with those of the bench plant experiment and the scale effect was small. Polymer deposit to the reactor wall limited a period of continuous operation of the plant. The amount of deposited polymer was increased with the square of reaction time. The rate of polymer deposit was proportional to polymer concentration and to the cube of pressure. The polymer deposit cannot be solved in the bulk process.     

Conformation of polyacrylamide in aqueous solution with interactive additives and cosolvents

The viscosity of polyacrylamide (PAM) dilute aqueous solutions with NaCl, glucose, and SDS as additives was measured by Ubbelohde viscometry. There was linear relationship between reduced viscosity vs. PAM concentration in aqueous solutions. The Huggins constant k and intrinsic viscosity [η] were used to study the conformation of the polymer chains and the degree of polymer–solvent interaction. In addition, the viscosity of diluted PAM solutions in water with acetone, ethanol, DMF, and ethylene glycol as cosolvent was measured. It was found that the polymer chain conformation contracted as the acetone, ethanol, and DMF cosolvent composition ratio increased, but there was no distinguishing difference between water–ethylene glycol compositions. The solution properties of PAM were used to estimate the swelling properties of PAM gel in the same external conditions, as gel is formed by crosslinking of linear polymer. In good solvent the polymer chain should be expanded, and gel is expected to have large swelling ratio. In water cosolvent systems, when the linear polymer chain underwent coil–globule transition, PAM gel should have volume phase transition under corresponding external conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3122–3129, 2003     

Characterization of poly(methyl methacrylate) from radiation-induced polymerization in the presence of a kaolin clay substrate

Two types of polymer are formed in the radiation-initiated polymerization of methyl methacrylate (MMA)–kaolin clay complexes. Homopolymer can be extracted from the complex by the use of organic solvents. Inserted polymer must be removed by dissolution of the polymer–clay complex with hydrofluoric acid. The polymers formed show no differences in structure (as determined by infrared analysis), had high molecular weights (1–5 × 10⁶), and had similar molecular weight distributions (as determined by GPC). The molecular weights of the homopolymer increased as temperature increased (25°–75°C), and dose rate decreased (24.9–7.35 rads/sec). The isotacticity of the polymers when compared to irradiated bulk polymer decreased as follows: inserted > homo > bulk. The compressive properties of the irradiated composite compared well with those of commercial bulk polymers. Degradation temperatures were 20° to 30°C higher for the composite than for the commercial chemically initiated bulk polymer.     

The sorption of poly(vinyl acetate) on cellulose. I. The nature and extent of the sorbed layer

The sorption of poly(vinyl acetate) from benzene solution onto cellulose fibers has been investigated with particular attention to the nature and extent of the sorbed layer of polymer. The cellulose substrate has been varied by swelling pretreatments with water, ethylenediamine, and 18% sodium hydroxide. The density of the sorbed polymer after drying was found to be similar to that of the bulk polymer (1.19–1.20 g/cm³). Water vapor sorption isotherms were used to evaluate the internal surface of cellulose and the decrease in the surface area accessible to water after sorption of the polymer. This decrease was considered equivalent to the area covered by sorbed polymer. The amount of polymer sorbed per unit area (5.0–5.5 mg PVAc sorbed from benzene per 1 m² of cellulose surface) was found to be substantially independent of the amount of sorbed polymer and of the swelling pretreatment, indicating that the thickness of the sorbed layer was quite uniform (40–50 Å). A comparison of the thickness of the sorbed layer in the dry state with the thickness of a monolayer with polymer molecules lying flat on the solid surface indicated that the fraction of the polymer segments attached directly to the surface was about 0.10. The amount of polymer sorbed per unit area of cellulose and consequently the thickness of the sorbed layer and the fraction of attachment can be affected by the nature of the solvent from which the polymer is sorbed.     

Copolymerization of bromophenylmaleimide with ethyl or butyl methacrylate

N‐p‐Bromophenylmaleimide (BrPMI) does not polymerize in solution by conventional free radical mechanism. However, it readily polymerized in bulk when mixed with a free radical initiator and heated in a microwave oven for 7–8 min. Copolymerization of ethyl methacrylate or butyl methacrylate with BrPMI was conducted in dioxane. The copolymers were characterized by IR and ¹H NMR spectroscopy and gel permeation chromatography. The monomer reactivity ratios were calculated by a non‐linear least‐square analysis. Thermal analysis indicated a great improvement in thermal stability of the copolymers compared with the methacrylate homopolymers. BrPMI was also polymerized in bulk in the DSC pan, which allowed the calculation of the activation energy of its polymerization. Copyright © 2003 Society of Chemical Industry     

Mechanical properties of a cryogenically mechanically alloyed polycarbonate–poly(aryl ether ether ketone) system

The processing–property relationship of a model cryogenically mechanically alloyed polymer–polymer system [polycarbonate (PC) and poly(aryl ether ether ketone) (PEEK)] was investigated. PC and PEEK powders were cryogenically mechanically alloyed for 10 h, and the resulting two‐phase powder particles were processed into testable coupons with a miniature ram‐injection molder. The bulk mechanical properties of the coupons made from the mechanically alloyed powders and nonmechanically alloyed powders were investigated as a function of mechanical alloying and injection‐molding parameters. The injection‐molded coupons were mechanically tested in the three‐point‐bending mode. The results demonstrated that no measurable improvement was achieved in the energy to break, strain at failure, or failure strength in the coupons made from the mechanically alloyed materials in comparison with those of the coupons made from the nonmechanically alloyed powders. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1196–1202, 2003     

Pervaporation performance of PTMSP membranes at high temperatures

The separation of ethanol–water mixtures by pervaporation has been carried out through poly(1‐trimethylsilyl‐1‐propyne) (PTMSP) membranes. This polymer is known to be alcohol‐selective and shows high selectivity and ethanol permeation rate. The performance of this polymer was studied at high temperatures over long periods of time to examine deterioration of its transport properties. The PTMSP membrane shows an initial separation factor (α) of about 10.7 and specific permeation rate (R) of 0.054 g m m^?2 h^?1 for a 10 wt % ethanol solution. Although this polymer has good characteristics for the separation of gases and liquid mixtures, its selectivity decreases with operating time, reaching a value of 8 after 450 h. On the other hand, the specific permeation rate remains almost constant except during the swelling period, in which it decreases to a value of 0.035 g m m^?2 h^?1. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2255–2259, 2003