Unperturbed dimensions of polystyrene derivatives. II. Poly-3,4-dichlorostyrene and poly-p-cyclohexylstyrene

The relationship of intrinsic viscosity to the number-average molecular weight has been obtained for poly-3,4-dichlorostyrene and poly-p-cyclohexylstyrene in a few solvents. Values of (〈L²〉₀/M)^1/2 have been estimated for poly-3,4-dichlorostyrene and poly-p-cyclohexylstyrene through the use of the treatment of Stockmayer and Fixman. The values of (〈L〉₀/M)^1/2 have been obtained as 2.18 ± 0.08 and 2.52 ± 0.07 for poly-3,4-dichlorostyrene and poly-p-cyclohexylstyrene, respectively. The σ value of a series of polystyrene derivatives has been found to increase with the bulk of side groups. This seems to indicate that the σ value is mainly determined by the steric repulsion between side groups.     

Gas-chromatographic determination of chlorostyrene and dichlorostyrene isomers in workplace air

Conditions for a gas-chromatographic determination of vapors and aerosols of p-chlorostyrene and 2,6-dichlorostyrene contained in workplace air samples were determined. The method is based on the adsorption of p-chlorostyrene and 2,6-dichlorostyrene on activated charcoal and fiberglass, desorption with toluene and analysis of the obtained solution by capillary gas chromatography with flame ionization detection (FID). The determination limit of the method is 5 mg m(-3) for each substance.     

FREE-RADICAL-INITIATED COPOLYMERIZATION OF 2-CHLOROSTYRENE, 4-CHLOROSTYRENE,AND 2,6-DICHLOROSTYRENE WITH MALEIC ANHYDRIDE

The title copolymers have been prepared by the free-radical-initiated copolymerization of 2-chlorostyrene (2-ClSt), 4-chlorostyrene (4-ClSt) and 2,6-dichlorostyrene (2,6-DClSt) with maleic anhydride (MAn) in toluene at 65°C. Copolymers of chlorinated styrenes with MAn prepared under different monomer-to-monomer ratios in the feed have alternating composition. In all cases, the mixture of comonomers forms charge-transfer complex monomers (CTC). The initial rate of copolymerization increases with the increase of electron donors in the comonomer feed, and the highest rates were at the equimolar ratios of comonomers in the feed. The thermal stability of the polymers was measured by thermogravimetric analysis in nitrogen. Homopolymers decompose by a one-step mechanism, while copolymers are more thermostable and decompose by a two-step mechanism. Glass transition temperatures (T_gs) of homopolymers are lower than T_gs of copolymers. The number and weight average molecular weights of chlorinated copolymers are higher than those of the corresponding homopolymers.     

Can Propagation Reaction in Carbocationic Polymerization and Copolymerization of Styrene be Diffusion Controlled ?

Summary: The reactivity ratios r₁ and r₂ in copolymerizations of styrene and parasubstituted styrenes, for which r₁ = 1/r₂, are in contradiction with diffusion control for their propagation reactions. The cross propagation rate constants k_12copol in copolymerization of styrene with p-chlorostyrene, p-methylstyrene and p-methoxystyrene have been shown to increase with their nucleophilicity parameter N. This is also not compatible with diffusion controlled cross propagation and propagation, but agrees with similar rate constants of propagation for these monomers. The capping rate constants k_12capp of reactions of poly(p-methylstyrene)^± and poly(p-methoxystyrene)^± with π-nucleophiles also increase with N, but with a much larger selectivity. This shows that k_12copol and k_12capp are not identical. The k, from 10⁹ to 6 10⁹ L mol⁻¹ s⁻¹, obtained with p-chlorostyrene, styrene and p-methylstyrene by the Diffusion Clock (DC) method are not consistent with those derived from the ionic species concentration (ISC method) for indene, 2,4,6-trimethylstyrene and p-methoxystyrene of the order of 10⁴ – 10⁵ L mol⁻¹ s⁻¹, also measured for living polymerization. These last values are in agreement with those measured previously in nonliving systems, and with an approximate compensation between the reactivity of a monomer and that of the corresponding carbocation.     

Flow injection analysis with in-line solid phase extraction for the spectrophotometric determination of sulfonated and unsulfonated Quinoline Yellow in Cologne

An integrated solid-phase spectrophotometry/ FIA  method is  proposed for the determination of the synthetic colorant matter Quinoline Yellow (QYWS) in the presence of its unsulfonated derivative QYSS. The procedure is based on the retention and preconcentration of the low level QYSS on a C-18 silica gel minicolumn, followed by sequential measurement of its absorbance at λ = 410 nm after its elution with methanol. The applicable concentration range, the detection limit and the relative standard deviation were the following: for QYWS, from 0.10 to 30.0 mg L^–1; 0.013 mg L^–1; and 0.6%; and for QYSS, between 10 and 1,000 μg L^–1; 2 μg L^–1; and 1.3%, respectively. The method was applied to the determination of small amounts of QYSS present in QYWS in Colognes. Percentages of recovery between 98% and 99% were obtained in all instances. The method was also satisfactorily applied to the determination of these compounds in samples of commercial Colognes comparing the results for QYWS with those offered by an HPLC reference method and also validating the results chemometrically. Received: 21 January 2000 / Revised: 17 March 2000 / Accepted: 22 March 2000     

Effects of complexing agents in radical copolymerization

Radical copolymerization of methyl methacrylate (MMA, M₁) with various monomers has been studied in presence of modifiers, i.e., complexing agents (CA): ZnCl₂, AlCl₃, AlBr₃, Al(C₂H₅)₂Cl, forming coordinate complexes with ester group of the monomer and of the propagating radical. The comonomers of the first group form complexes of similar structure and stability as MMA, methyl acrylate, or butyl acrylate. The comonomers of the second group do not form complexes with the modifiers (vinylidene chloride, 2,6-dichlorostyrene, p-chlorostyrene, styrene). For all systems studied the copolymer composition follows the Mayo-Lewis equation. In the first group of the systems the effective reactivity ratios (r₁, r₂) approach unity with increase of the CA molar content (r₁ = r₂ ? 1 at [(CA)/MMA] + [MA] ≥ 0,3) In the second group of the systems the values of r₁ either increase to a limit value (at [CA]/[MMA] ≥ 0.3), pass through maximum, or decrease to a limiting value with the CA molar content. The values of r₂ decrease in all systems. The character of variation of r₁ and r₂ has been explained in terms of effects of the CA's on reactivity of MMA and PMMA radical. The equations for the copolymer compositions in these systems have been derived.     

Effect of substituents in the styrene ring on the dynamic mechanical relaxations of a styrene-crosslinked unsaturated polyester resin

The dynamic mechanical properties of a series of polyester resins made from a maleic/phthalic anhydride-based unsaturated polyester crosslinked with each of styrene, 4-methyl styrene, 4-ethyl styrene, 4-n-butyl styrene, 4-isopropyl styrene, tertiary butyl styrene, 4-chlorostyrene, and 3,4-dichlorostyrene were studied. The order of the α transition temperatures was as expected from that for the homopolymers, except in the case of the chlorostyrenes, for which dipolar interactions with the polyester chain may be important. The styrene bridges appeared to be involved in a steric interaction (and in the case of the chlorostyrenes, a dipolar interaction) with the β relaxing ester species. It is suggested that both the γ and γ′ relaxations involve similar interactions between the matrix and the relaxing moieties. For the 4-n-butyl styrene resin, an additional relaxation below ?170°C was observed, and is ascribed to relaxation of the n-butyl group.     

Investigation of the colour reaction of phenols with MBTH,II: Properties of the isolated products of the reaction with phenol, 2,6-dimethylphenol and 4-methylphenol

The following model compounds for the study of the oxidative coupling reactions of 2-hydrazono-3-methylbenzothiazoline (MBTH) with phenolic compounds were prepared: thep-coupling products of the reagent with phenol and 2,6-xylenol and theo-coupling product withp-cresol. The proposed structure of the dyes was confirmed. In strongly polar and ionic media the azobetaine form of the products predominates, and in non-polar media the azine structure. The principal physico-chemical properties of the products were determined and the results contributed to formulation of the course of the coupling reaction, and to optimization of the conditions for determination of small amounts of phenolic substances. The violeto-coupling product is less stable than the redp-coupling products, and intramolecularly hydrogen-bonded six-membered ring is assumed to exist in the structure. In acid medium the dyes are mainly monoprotonated, and partly diprotonated in concentrated sulphuric acid medium. The products are stable up to about pH 11. These properties make extraction into low-polarity solvents possible. The dye derived from 2,6-xylenol andp-cresol has not hitherto been prepared. The principal spectral characteristics, _max(), of the products in ethanol medium are: 499 nm (4.7 × 10⁴ 1·mole^–1 cm^–1) for the phenol derivative, 486 nm (5.0 × 10⁴) for the 2,6-xylenol product, and _max 540 nm for thep-cresol product.Part I: Mikrochim. Acta [Wien]1977,I, 241     

Phase behavior in copolymer blends of poly (p-chlorostyrene-co-o-chlorostyrene) and phenylsulfonylated poly (2,6-dimethyl-1,4-phenylene oxide)

The miscibility of random copolymers of o-chlorostyrene and p-chlorostyrene [P (oClSt-co-pClSt)] with partially phenylsulfonylated poly (2,6-dimethyl-1,4-phenylene oxide) (SPPO) copolymers has been studied, using differential scanning calorimetry (DSC) to establish T_g behavior. It already has been established that the isomeric effect of the chlorine substitution on miscibility is large. Thus the para-chloro-substituted styrenic homopolymer is miscible with all SPPOs containing more than ～ 5 mol % phenylsulfonylation, whereas the ortho-chloro-substituted homopolymer is immiscible with the entire range of SPPO copolymer compositions (and also with the respective homopolymers). As a result of this asymmetric behavior of the homopolymers, the width of the window of miscibility in blends now investigated containing copolymers with high pClSt content and SPPO is much greater than in the corresponding blends containing copolymers with large mole fraction of oClSt. These differences are reflected in the corresponding χ parameters calculated from analysis of the data. It was also found that the miscibility is temperature dependent and that the regime in the copolymer-copolymer composition plane shrank as the equilibrium temperature increased, results indicative of LCST behavior. © 1994 John Wiley & Sons, Inc.     

Determination of the Mg-Concentration Profile in Near-Surface Layers of Materials Using the 24Mg(α,p)27Al Nuclear Reaction

 The ²⁴Mg(α, p)²⁷ Al nuclear reaction was applied for the determination of the magnesium distribution in near-surface layers of materials. The cross sections of this reaction were determined in the energy region between 4.5 and 5.5 MeV in steps of 5 to 10 KeV (θ_lab : 158°) using thin magnesium films. The investigated projectile energy region included five main resonances allowing the determination of magnesium. The uncertainty of the cross-section determination was of the order of 7%. The applicability of the technique was tested using Mg-implanted AISI 321 steel samples. Depth resolution of 100 nm and detection limits of the order of 0.1 ppm were achieved for the determination of magnesium in steel samples using the 4805 keV resonance of the ²⁴Mg(α, p)²⁷ Al nuclear reaction. The shape and height of the magnesium depth-profile in the Mg-implanted steel samples were compared with corresponding values obtained by X-ray photoelectron spectroscopy. Received July 15, 1999. Revision March 30, 2000.     

Simultaneous determination of five common additives in insulating mineral oils by high‐performance liquid chromatography with ultraviolet and coulometric detection

Dielectric mineral oils are used to impregnate power transformers and large electrical apparatus, acting as both liquid insulation and heat dissipation media. Antioxidants and passivators are frequently added to mineral oils to enhance oxidation stability and reduce the electrostatic charging tendency, respectively. Since existing standard test methods only allow analysis of individual additives, new approaches are needed for the detection of mixtures. For the first time we investigate and discuss the performance of analytical methods, which require or do not require extraction as sample pretreatment, for the simultaneous reversed‐phase high‐performance liquid chromatography determination of passivators (benzotriazole, Irgamet^® 39) and antioxidants (N‐phenyl‐1‐naphtylamine, 2,6‐di‐tert‐butylphenol, 2,6‐di‐tert‐butyl‐p‐cresol), chosen for their presence in marketed oils. Quick easy, cheap, effective, rugged and safe and solid phase extractions were evaluated as sample pretreatments. Direct sample‐injection was also studied. Ultraviolet spectrophotometry and direct‐current coulometry detection were explored. As less prone to additive concentrations variability, the direct‐injection high‐performance liquid chromatography with ultraviolet and coulometric detection method was validated through comparison with Standard Method IEC 60666 and through an ASTM interlaboratory proficiency test. Obtained detection limits are (mg kg^?1): benzotriazole (2.8), Irgamet^® 39 (13.8), N‐phenyl‐1‐naphtylamine (11.9), 2,6‐di‐tert‐butylphenol (13.1), 2,6‐di‐tert‐butyl‐p‐cresol (10.2). Simultaneous determination of selected additives was possible both in unused and used oils, with good precision and accuracy.     

Miscibility and phase behavior in atactic polystyrene and poly(o-chlorostyrene-co-p-chlorostyrene) blends: Effect of polystyrene molecular weight and copolymer composition

Miscibility in blends of random copolymers of o-chlorostyrene and p-chlorostyrene [P(oClSy-co-pClS_1-y)] with 8 atactic polystyrene (aPS) fractions has been studied at temperatures ranging from 150°C to 300°C. Miscibility windows whose size depends on the molecular weight of the PS and on the copolymer composition, y, were observed for each blend. From these data, the temperature dependence of the three segmental interaction parameters required to describe this system were obtained.     

Determination of nicotinamide (NA) using its polarographic catalytic wave in the presence of KIO3

Nicotinamide (NA) yields a polarographic catalytic wave with a peak potential –1.38 V (vs. SCE) in 0.1 mol/L HAc-NaAc (pH 4.7)/4 × 10^–3 mol/L KIO₃ buffer solution. The sensitivity of the catalytic wave increased in one order of magnitude as compared to that of the responding reduction wave without KIO₃. Based on this observation, a new method for the determination of NA was recommended. The second order derivative peak current was proportional to the NA concentration in the range of 5 × 10^–8 – 6 × 10^–7 mol/L. 0.11-fold vitamin B₁, 0.13-fold B₂, 0.14-fold B₆ and 8-fold nicotinic acid amounts do not interfere the determination of 1 × 10^–6 mol/L NA. The proposed method was used to determine the NA content in multivitamin tablets, with good agreement to the declared amount. Received: 25 October 1999 / Revised: 28 March 2000 / /Accepted: 31 March 2000     

Conformational behavior of styrene–p-chlorostyrene triblock copolymers in dilute solutions. I. Composition dependence of conformational behavior

Dilute solution properties of (styrene-p-chlorostyrene) triblock copolymers in various solvents were studied over a wide range of molecular weight and composition. Viscosity and osmotic pressure results indicate that the conformational behavior of the B_mA_nB_m and A_mB_nA_m copolymers (A = styrene; B = p-chlorostyrene; m and n denote the number of units) are similar in nonselective solvents such as toluene and 2-butanone, but different in selective solvents such as carbon tetrachloride and cumene. Short-range and long-range interaction parameters of the block copolymers were determined by applying the Stockmayer–Fixman method to viscosity data and also by application of the equation relating the osmotic virial coefficient and the excluded volume. The results show that the unperturbed dimensions of the block copolymers vary linearly with composition, and long-range interaction parameters in nonselective solvents can be expressed by those of the parent homopolymers, the chemical composition, and values of the interaction parameter β_AB between styrene and p-chlorostyrene monomeric units.     

The Extractive-Spectrophotometric Determination of Iron(III) As a Mixed-Ligand Complex with N-Hydroxy-N,N′DI-p-Tolyl-p-Toluamidine and Thiocyanate

The extractive-photometric determination or iron(III) as a mixed-ligand complex with N -hydroxy-N, N′ -di-p -tolyl-p -toluamidine (HDTTA) and thiocyanate is described. The orange-red Waterinsoluble 1:1:2 (metal: HDTTA: SCN^?) ternary complex formed in 0.1–0.6 M hydrochloric acid solutions is quantitatively extractable into benzene. The wavelength of maximum absorption, molar absorptivity and sensitivity of the colour system are 460nm, 12000 l. mole^?1 cm^?1 and 0.0046 μg Fe/cm ²respectively. The influence or foreign ions on the determination of iron has been studied. This method has also been applied to determine the iron content of several alloys.     

Copolymerization of 4-cyclopentene-1,3-dione with p-chlorostyrene and vinylidene chloride

The copolymerization of 4-cyclopentene-1,3-dione (M₂) with p-chlorostyrene and vinylidene chloride is reported. The copolymers were prepared in sealed tubes under nitrogen with azobisisobutyronitrile initiator. Infrared absorption bands at 1580 cm.^?1 revealed the presence of a highly enolic β-diketone and indicated that copolymerization had occurred. The copolymer compositions were determined from the chlorine analyses and the reactivity ratios were evaluated. The copolymerization with p-chlorostyrene (M₁) was highly alternating and provided the reactivity ratios r₁ = 0.32 ± 0.06, r₂ = 0.02 ± 0.01. Copolymerization with vinylidene chloride (M₁) afforded the reactivity ratios r₁ = 2.4 ± 0.6, r₂ = 0.15 ± 0.05. The Q and e values for the dione (Q = 0.13, e = 1.37), as evaluated from the results of the vinylidene chloride case, agree closely with the previously reported results of copolymerization with methyl methacrylate and acrylonitrile and confirm the general low reactivity of 4-cyclopentene-1,3-dione in nonalternating systems.     

Valence 4p functions for the first-row transition metal atoms

For the valence 4p orbitals of the first-row transition metal atoms Sc through Zn, Gaussian-type basis functions are developed referring to excited 3d ^m 4s ¹4p ¹ electronic configurations. Molecular tests of the present work 4p sets are performed for the Cu atom, the diatomic Cu₂ molecule, and Cu₉ and Cu₁₃ clusters, and the results are compared with those from two literature sets. Received: 17 January 2000 / Accepted: 30 May 2000 / Published Online: 11 September 2000     

Separation of trace amounts of rhodium(III) with tri-n-butyl phosphate from nitric acid and sodium trichloroacetate media

A new method for the quantitative extraction and separation of trace amounts of rhodium from nitric acid and sodium trichloroacetate media has been established based on the formation of an ion-association complex of hexahydrated rhodium cation Rh(H₂O)₆ ³⁺ and the trichloroacetate (TCA) anion in tri-n-butyl phosphate (TBP). The effect of various factors (solvent, pH, sodium trichloroacetate, shaking time, phase volume ratio, composition of the extracted species, foreign ions, transformation of rhodium chlorocomplexes into hexahydrated cation, etc.) on the extraction and back-extraction of rhodium has been investigated. The method can be combined with subsequent FAAS determination of rhodium. The procedure was applied to determine rhodium traces in chloroplatinic acid and palladium chloride. Received: 17 March 2000 / Revised: 15 May 2000 / Accepted: 19 May 2000     

Dynamics of macromolecular chains. V. Interpretation of the dielectric relaxation data

The autocorrelation function of orientations, derived for the model of conformational jumps in a chain described in a tetrahedral lattice, has been tentatively applied to dielectric relaxation data. The complex dielectric relaxation of polymers can be interpreted by the aid of only two relaxation processes. In the case of poly(p-chlorostyrene) in solution, the characteristic times that we have calculated agree favorably with the fluorescence-depolarization results. The model has been shown to be consistent with the empirical decay function exp[? (t/τ)^β] proposed by Williams.