Dark cure studies of cationic photopolymerizations of epoxides: Characterization of kinetic rate constants at high conversions

The effective propagation rate constant (k_p; averaged over all the propagating active centers) was characterized for solvent‐free cationic photopolymerizations of phenyl glycidyl ether over the entire range of conversions, including the high conversion regime in which mass transfer limitations become important. The profile for the k_p as a function of conversion was found to exhibit a constant plateau value at low to intermediate conversions, followed by a monotonic increase above a threshold value of conversion. To explain this trend, it is proposed that at high conversion the diffusional mobility of the photoinitiator counterion is reduced whereas the mobility of the cationic active center remains high because of reactive diffusion. Therefore, with increasing conversion, the average distance between the active centers and counterions may increase, resulting in an increase in the propagation rate constant. The profiles for the k_p values were investigated as a function of the temperature, photoinitiator anion, and photoinitiator concentration. As the photoinitiator concentration was increased, the plateau value of the effective propagation rate constant decreased whereas the threshold conversion increased. All of the experimental trends are consistent with the proposed increase in ion separation at high conversions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4409–4416, 2004     

Photopolymerization of 1,6‐hexanedioldiacrylate initiated by three‐component systems based on N‐arylphthalimides

Three‐component photoinitiators comprised of an N‐arylphthalimide, a diarylketone, and a tertiary amine were investigated for their initiation efficiency of acrylate polymerization. The use of an electron‐deficient N‐arylphthalimide resulted in a greater acrylate polymerization rate than an electron‐rich N‐arylphthalimide. Triplet energies of each N‐arylphthalimide, determined from their phosphorescence spectra, and the respective rate constants for triplet quenching by the N‐arylphthalimide derivatives (acquired via laser flash photolysis) indicated that an electron–proton transfer from an intermediate radical species to the N‐arylphthalimide (not energy transfer from triplet sensitization) is responsible for generating the initiating radicals under the conditions and species concentrations used for polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4009–4015, 2004     

Preparation of macromonomers by copolymerization of methyl acrylate dimer involving β fragmentation

The unsaturated dimer of methyl acrylate [CH₂C(CO₂CH₃)CH₂CH₂CO₂CH₃, or MAD] was copolymerized with various monomers to prepare copolymers bearing the ω-unsaturated end group [CH₂C(CO₂CH₃)CH₂ ] arising from β fragmentation of the MAD propagating radical. Copolymerizations of MAD with cyclohexyl and n-butyl acrylate resulted in copolymers with ω-unsaturated end groups, and increasing the temperature up to 180 °C resulted in an increase in the rate of β fragmentation of MAD radicals relative to propagation. Only a small amount of unsaturated end groups was introduced by copolymerization with ethyl methacrylate (EMA), and the EMA content in the copolymer increased with temperature. These findings could be explained by the reversible addition of the poly(EMA) radical to MAD. The copolymerization with ethyl α-ethyl acrylate (EEA) did yield a copolymer containing unsaturated end groups with MAD units as part of the main chain, although the steric hindrance of the ethyl group suppressed homopropagation and crosspropagation of EEA, resulting in low polymerization rates. Therefore, the copolymerization of MAD with acrylic esters at high temperatures was noted as a convenient route for obtaining acrylate–MAD copolymers bearing unsaturated end groups at the ω end (macromonomer). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 597–607, 2004     

Combined effects of clay modifications and compatibilizers on the formation and physical properties of melt‐mixed polypropylene/clay nanocomposites

The melt mixing technique was used to prepare various polypropylene (PP)‐based (nano)composites. Two commercial organoclays (denoted 20A and 30B) served as the fillers for the PP matrix, and two different maleated (so‐called) compatibilizers (denoted PP‐MA and SMA) were employed as the third component. The results from X‐ray diffraction (XRD) and transmission electron microscope (TEM) experiments revealed that 190 °C was an adequate temperature for preparing the nanocomposites. Nanocomposites were achieved only if specific pairs of organoclay and compatibilizer were simultaneously incorporated in the PP matrix. For example, PP/20A(5 wt %)/PP‐MA(10 wt %) and PP/30B(5 wt %)/SMA(5 wt %) composites exhibited nanoscaled dispersion of 20A or 30B in the PP matrix. Differential scanning calorimetry (DSC) results indicated that the organoclays served as nucleation agents for the PP matrix. Generally, their nucleation effectiveness increased with the addition of compatibilizers. The thermal stability enhancement of PP after adding 20A was confirmed with thermogravimetric analysis (TGA). The enhancement became more evident as a suitable compatibilizer was further added. However, for the 30B‐included composites, thermal stability enhancement was not evident. The dynamic mechanical properties (i.e., storage modulus and loss modulus) of PP increased as the nanocomposites were formed; the properties increment corresponded to the organoclay dispersion status in the matrix. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4139–4150, 2004     

Behavior and surface energies of polybenzoxazines formed by polymerization with argon,oxygen, and hydrogen plasmas

Polybenzoxazine (PBZZ) thin films can be fabricated by the plasma‐polymerization technique with, as the energy source, plasmas of argon, oxygen, or hydrogen atoms and ions. When benzoxazine (BZZ) films are polymerized through the use of high‐energy argon atoms, electronegative oxygen atoms, or excited hydrogen atoms, the PBZZ films that form possess different properties and morphologies in their surfaces. High‐energy argon atoms provide a thermodynamic factor to initiate the ring‐opening polymerization of BZZ and result in the polymer surface having a grid‐like structure. The ring‐opening polymerization of the BZZ film that is initiated by cationic species such as oxygen atoms in plasma, is propagated around nodule structures to form the PBZZ. The excited hydrogen atom plasma initiates both polymerization and decomposition reactions simultaneously in the BZZ film and results in the formation of a porous structure on the PBZZ surface. We evaluated the surface energies of the PBZZ films polymerized by the action of these three plasmas by measuring the contact angles of diiodomethane and water droplets. The surface roughness of the films range from 0.5 to 26 nm, depending on the type of carrier gas and the plasma‐polymerization time. By estimating changes in thickness, we found that the PBZZ film synthesized by the oxygen plasma‐polymerization process undergoes the slowest rate of etching in CF₄ plasma. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4063–4074, 2004     

A new method for atmospheric nitrogen dioxide measurements using the combination of a stripping coil and fluorescence detection.

A new stripping coil for the collection of nitrogen dioxide (NO2) has been developed to increase its versatility and efficiency. Nitrogen dioxide measurements based on quantitative collection through a reaction coil into an alkaline solution has been examined. Nitrogen dioxide is collected in a 0.1 N NaOH solution. This collection system has an efficiency of nearly 100%. The absorbed nitrogen dioxide has been measured by fluorescence detection with sub-ppbv detection limits. The excitation wavelength at 360 nm and the produced emission wavelength at 405 nm were suitable for nitrite ion measurements.     

Differential pulse anodic stripping voltammetric determination of traces of copper with a tobramycin-Nafion modified electrode.

A Nafion-modified glassy carbon electrode incorporated with tobramycin for the voltammetric stripping determination of Cu2+ has been explored. The electrode was fabricated by tobramycin containing Nafion on the glassy carbon electrode surface. The modified electrode exhibited a significantly increased sensitivity and selectivity for Cu2+ compared with a bare glassy carbon electrode and the Nafion modified electrode. Cu2+ was accumulated in HAc-NaAc buffer (pH 4.6) at a potential of -0.6 V (vs. SCE) for 300 s and then determined by differential pulse anodic stripping voltammetry. The effects of various parameters, such as the mass of Nafion, the concentration of tobramycin, the pH of the medium, the accumulation potential, the accumulation time and the scan rate, were investigated. Under the optimum conditions, a linear calibration graph was obtained in the concentration range of 1.0 x 10(-9) to 5.0 x 10(-7) mol l(-1) with a correlation coefficient of 0.9971. The relative standard deviations for eight successive determinations were 4.3 and 2.9% for 1.0 x 10(-8) and 2.0 x 10(-7) mol l(-1) Cu2+, respectively. The detection limit (three times signal to noise) was 5.0 x 10(-10) mol l(-1). A study of interfering substances was also performed, and the method was applied to the direct determination of copper in water samples, and also in analytical reagent-grade salts with satisfactory results.     

Determination of nickel in alloys and plant leaves with salicylaldehyde 3-oxobutanoylhydrazone by spectrophotometry.

A simple and highly sensitive reagent of salicylaldehyde 3-oxobutanoylhydrazone (salicylaldehyde acetoacetic acid hydrazone, SAAH) was synthesized and studied for the spectrophotometric determination of nickel in detail. In the pH range 6, which greatly increased the selectivity, nickel reacted with SAAH to form a 1:1 yellow complex, having a sensitive absorption peak at 405 nm. Under the optimal conditions, Beer's law was obeyed over the range from 0.0117 to 0.1174 microg cm(-3). The apparent molar absorptivity was 3.025 x 10(5) dm3 mol(-1) cm(-1). The detection limit and the variation coefficient were found to be 1.752 ng cm(-3) and 1.0%, respectively. The method has been applied to the quantitative determination of nickel in different alloys and leaves.     

Enantiomeric separation of basic drugs with partially filled serum albumin as chiral selector in capillary electrophoresis.

A reliable method is presented for the chiral separation of three basic drugs (mexiletine, chlorpheniramine and propranolol) with serum albumins (human and porcine, HSA and PSA) as chiral selectors by capillary electrophoresis in combination with the partial filling technique. Based on the systematic optimization of operation variables, the chiral separation of mexiletine, chlorpheniramine and propranolol was achieved in the pH 7.4 phosphate buffer by using HSA, PSA and PSA as selectors, respectively. The chiral recognition ability of HSA and PSA was compared. HSA and PSA show a different chiral recognition ability for each of the three drugs. In addition, the association constants between enantiomeric drugs and proteins were determined to be 2.00 and 3.80 x 10(2) M(-1) for mexiletine and HSA, 0.59 and 1.12 x 10(3) M(-1) for chlorpheniramine and PSA, and 0.87 and 1.42 x 10(3) M(-1) for propranolol and PSA. The method for the chiral separation and determination of association constants possesses the advantages of simple performance, effective avoiding of the interference of the UV detection from protein, and lowering of the reagent consumption.     

Dynamic surface tension measurements of surfactant solutions using the maximum bubble pressure method – limits of applicability

One of the essential differences in the design of bubble pressure tensiometers consists in the geometry of the measuring capillaries. To reach extremely short adsorption times of milliseconds and below, the so-called deadtime of the capillaries must be of the order of some 10 ms. In particular, for concentrated surfactant solutions, such as micellar solutions, short deadtimes are needed to minimize the initial surfactant load of the generated bubbles. A theoretical model is derived and confirmed by experiments performed for a wide range of experimental conditions, mainly in respect to variations in deadtime and bubble volume.