Preparation of polyacrylate–polysiloxane core–shell latex particles

Crosslinked polymer seed latexes of butyl acrylate, methyl methacrylate and methacrylic acid were synthesized with ethylene glycol dimethacrylate as a crosslinking agent in a first step. Three different processes of seeded emulsion polymerization were used to prepare an outlayer of polysiloxane on the above seed latex particles: (A) direct anionic polymerization of D₄ (octamethyl tetracyclosiloxane) catalyzed by potassium hydroxide; (B) direct cationic polymerization of D₄ onto the seed catalyzed by dodecylbenzene sulfonic acid; (C) a vinyl-containing polysiloxane prepared by copolymerization of D₄ and vinyl septamethyl tetracyclosiloxane was added before the D₄ cationic polymerization. Characterization by transmission electron microscopy showed that only process C provided satisfactory results. Film hardness was measured, and the latex film from process C demonstrated the lowest hardness of all the films. The mechanism of polymerization is discussed.     

Photolysis of azomethane–propane mixtures. Arrhenius parameters for the hydrogen abstraction reactions of methyl with azomethane and with propane

Mixtures of up to 14% azomethane in propane have been photolyzed using mainly 366 nm radiation in the ranges of 323–453 K and 25–200 torr. Detailed measurements were made of the yields of nitrogen, methane, and ethane. Other products observed were isobutane, n-butane, ethene, and propene. A detailed mechanism is proposed and shown to account for the observed variation of product yields with experimental conditions. The quantum yield of the molecular process is found to be given by the temperature-independent equation The values of rate constants obtained are where the reactions are and it is assumed that the rate constant for the reaction is given by      

A novel phenyl–bromine ligand exchange reaction on germanium by boron tribromide

A novel phenyl–bromine ligand exchange reaction by BBr₃ on germanium was investigated that proceeds without breaking Ge CH₂Ar bond. Typically, the reaction between (PhCH₂)₃PhGe and BBr₃ resulted exclusively in the formation of (PhCH₂)₃GeBr. Copyright © 2005 John Wiley & Sons, Ltd.     

A model study of the efficiency of the Asp–His–Ser triad

The observation of the Asp–His–Ser triad (Asp: aspartate, His: histidine, Ser: serine) triad both in mammalian and bacterial proteases suggests a special efficiency. A series of B3LYP/D95*(d,p) calculations on various [X–H^βY]^? dyads (as part of the [X–H^βY–H^αAc]^? model triad, HAc: acetic acid) made from eight different anions X^? and 15 different coupling elements H^βY was done to analyze the molecular origin of this efficiency. The X^? anion acts merely as an electron density donor independent of its chemical nature, and the evolutionary selection of Asp for the catalytic triad therefore seems to be caused by the pH of the triads environment. As the linking proton H^β moves from Y^? to X^?, electron density is effectively moved from X^? to Y^? thereby increasing the proton affinity (PA) of the [X–HY]^? dyad, which finally leads to the deprotonization of the HAc molecule. The degree to which the position of H^α controls the PA is dominatly determined by the coupling element HY. The model calculations indicate that 4‐methyl‐1H‐imidazole (HMim) is a very efficient coupling element, which suggest that the evolutionary convergence to the Asp–His–Ser is not only controlled by the ready availability of the imidazole motive in His but also by its high efficiency. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

The effect of mixed solvents pyridine–carbon tetrachloride on the radical polymerization of methyl methacrylate

A study was made of the methyl methacrylate (MMA) solution polymerization in CCl₄-pyridine mixtures as well as in net components at 30, 50, and 70°C. The results obtained show that there are no significant deviations from additivity in the overall chain transfer constants that fit the straight line between the values of Cs for CCl₄ and pyridine. It can be concluded that the EDA interaction between CCl₄ and pyridine does not change the sensitivity of each component for chain transfer from propagation PMMA free radical. The pyridine in the system increases the rate of MMA polymerization as a result of the higher rate of initiation.     

Direct rotating-sector studies of the systems: Styrene–methyl methacrylate and styrene–methyl acrylate

The rotating-sector technique was applied directly in a study of two copolymerization systems: styrene–methyl methacrylate and styrene–methyl acrylate. The two coupled rate expressions which describe the change in radical concentrations for two-component polymerizations degenerate into a single expression identical in form to the radical expression for a homopolymerization when the ratio of the radical concentrations under intermittent illumination is assumed constant and equal to the ratio under steady illumination. Numerical solutions of the complete rate expression by use of constants from the literature confirm that this assumption is valid for a rotating-sector experiment. The overall lifetimes of these two-component systems were defined and measured experimentally as a function of monomer composition and then compared with lifetimes calculated by using literature rate constants. The agreement was satisfactory. The direct application of the technique to the two-component system provides an independent experiment which for some systems seems to be more sensitive to the value of the cross-termination constant than the usual steady-state method.     

Photolysis of 1,1,1-trifluoromethylazomethane as a source of methyl and trifluoromethyl radicals

The photochemistry of 1,1,1-trifluoromethylazomethane has been partially characterized. The quantum yield for N₂ formation from photolysis at 366 nm and room temperature was unity at low pressure and decreased to 0.5 at 630 torr. At room temperature the principal products were C₂H₆, C₂F₆, CH₃CF₃ (or CH₂CF₂ + HF at reduced pressures), plus substituted hydrazines, which mainly arise from addition of CF₃ to the parent followed by combination of these radicals with CH₃ or CF_3. These fluorinated methyl hydrazine products detract from the general utility of CF₃-N₂-R compounds as sources for simultaneous study of the chemistry of CF₃ and R radicals. At room temperature the hydrazine products accounted for more than 50% of the total yield; however, these products can be reduced by lowering the temperature and at 195°K their yields are negligible. The quantum yield for intramolecular (direct) formation of CH₃CF₃ + N₂ was shown to be ≤0.002.     

Spin-Free Quantum Chemistry. XXI. Hartree–Fock theory

The theory of the open-and closed-shell restricted Hartree–Fock method is given a unitary group formulation. Both extremum and stability conditions are employed, the former leading to a generalized Brillouin theorem.     

Adsorption of polymers at the solution–solid interface. V. Styrene–methyl methacrylate copolymers on carbon

The adsorption of a series of block and random styrene–methyl methacrylate copolymers on an animal charcoal and on Graphon has been studied. On charcoal, adsorption decreases with increase of molecular weight because of the inability of larger coils to penetrate into the adsorbent. An analysis is presented which requires that coils undergo considerable distortion on adsorption in pores. The adsorption of random copolymers on Graphon is also in reverse order of molecular weight; this effect may be due to particle bridging leading to the formation of interparticle “pores.” The relative affinity of the styrene and methyl methacrylate residues is different on charcoal and Graphon, respectively; on both surfaces, however, relatively few of the more active residues are required for adsorption. Block and random copolymers are adsorbed to different extents which depend on the nature of the adsorbent surface.     

聚硅氧烷增容母料的制备及应用

火工品引爆时所释放的能量会对结构施加瞬时超过载的冲击,单一的硅橡胶硫化胶缓冲器不能满足阻尼材料性能的使用要求,纯硅橡胶单一硫化或共混硫化胶的损耗因子不足0．15,对应的温域非常小。聚硅氧烷呈螺旋状,表面张力低,但直接使用与其它聚合物相容性差。将硅氧烷进行丙烯酸酯类接枝共聚,可以保持其低温阻尼性能改善高温阻尼性能和拓宽阻尼温域。本文以软聚合物聚硅氧烷为核、硬聚合物丙烯酸酯类为壳,通过乳液接枝共聚的方法制备出具有“强制互容     

Polymerization of methyl methacrylate in a tetrahydrofuran–maleic anhydride system. Part II

A donor–acceptor complex consisting of tetrahydrofuran and maleic anhydride initiates photochemical and thermal polymerization of methyl methacrylate. The mechanism of the transformation of this complex was investigated by studying changes in its electrical conductivity, its chemiluminescence, and various influences on its initiating capability (water, air, DPPH, substitution of styrene for methyl methacrylate and of 1,4-dioxane for tetrahydrofuran). It has been shown that initiation by radicals cannot be clearly excluded and that ionic radicals form in the system and can initiate the anionic growth of the chain.     

Chromatographic properties of various polysiloxane stationary phases for separation of 2,3,7,8–chloro-substituted dibenzo-p-dioxin and dibenzofuran isomers–a systematic comparison

Glass capillaries coated with four crosslinked and surface-bonded OH-terminated polysiloxanes [PS 347.5, OV-17-OH, OV-225-OH, and OV-240-OH] were compared with commonly used methyl-terminated SP-2330-coated columns with respect to their selectivity for the separation of 2,3,7,8-chloro-substituted dibenzo-p-dioxins and dibenzofurans. The methyl- and phenyl-substituted phases [PS 347.5 and OV-17-OH] exhibit only moderate isomer selectivity which limits their applicability in this field. The examined 3-cyanopropyl-substituted phases [OV-225-OH, OV-240-OH, and SP-2330] allow complete separation of all 2,3,7,8-chlorosubstituted PCDDs and PCDFs. With SP-2330 longer columns are required (50 m) for baseline separation of critical groups of isomers. OV-225-OH was found to be the most suitable phase as to isomer selectivity. In comparison to SP-2330, the analysis times can be reduced by a factor of two.     

Dilute solution properties of styrene–acrylonitrile and styrene–methyl methacrylate copolymers. I. Intrinsic viscosity–molecular weight relations

Styrene–acrylonitrile (St–AN) copolymers of three compositions—27.4 mole-% (SA₁); 38.5 mole-% (SA₂); and 47.5 mole-% (SA₃) acrylonitrile—and styrene–methyl methacrylate (St–MMA) copolymer (SM) of 46.5 mole-% methyl methacrylate were prepared by bulk polymerization at 60°C with benzoyl peroxide as the initiator, and were then fractionated. The molecular weights of unfractionated and fractionated samples were determined by light scattering in a number of solvents. The [η] versus M?_w relations at 30°C were established for SA₁, SA₂, SM, and polystyrene (PSt) in ethyl acetate (EAc), dimethyl formamide (DMF), and γ-butyrolactone (γ-BL), and for SA₃ in methyl ethyl ketone (MEK), DMF, and γ-BL. Second virial coefficients A₂ and the Huggins constant were determined. From values of A₂ and the exponent a of the Mark–Houwink relation it is seen that the solvent power for samples SA₁, SA₂, and PSt is in the order EAc < γ-BL < DMF, while for sample SA₃ the solvent power is in the order MEK < γ-BL < DMF. The solvent power decreases with an increase in AN content. The solvent power of the three solvents used for SM copolymer sample is practically the same within experimental errors. From the a values it is concluded that in a given solvent the copolymer chains are more extended than the corresponding homopolymers.     

Synthesis of 32‐phenyl‐substituted methyl E/Z‐pyropheophorbide‐a's from methyl E/Z‐pyropehophorbide‐a 131‐ketoximes

Methyl E/Z‐pyropheophorbide‐a 13¹‐ketoximes 2a,b and their O‐acetyl derivatives 3a,b were oxidized with osmium(VIII) oxide to give aldehydes 4a,b and 5a,b , respectively. The Wittig reactions of the aldehyde chlorines 4a,b and 5a,b with benzyltriphenylphosphonium chloride were performed to form the corresponding methyl (3¹E/Z,13¹E/Z)‐3²‐phenylpyropheophorbide‐a 13¹‐ketoximes 6aa‐bb and their O‐acetyl derivatives 7aa‐bb ; hydrolysis of these ketoximes 6aa,ba and 6ab,bb in formic acid produced methyl (E/Z)‐3²‐phenylpyropheophorbide‐a's 8a,b .     

Photopolymerization initiated by charge–transfer complex. X. Photopolymerization of methyl methacrylate with the use of isoquinoline–sulphur dioxide charge–transfer complex

Aqueous polymerization of methyl methacrylate in visible light was studied using isoquinoline–sulphur dioxide (IQ–SO₂) charge–transfer complex as the photoinitiator. Analysis of kinetic and other data indicate that the polymerization proceed via a radical mechanism and the termination is dependent on the initiator concentration. Chain–termination via degradative chain (initiator) transfer appears to be predominant here.     

Retention on mixed cyclodextrin/polysiloxane stationary phases in capillary GC—Evidence for the interaction of cyclodextrin and polysiloxane

The dependence of the retention on stationary phases consisting of mixtures of a cyclodextrin (perpentyl-β-cyclodextrin) and a polysiloxane (cyanopropyl-7%-, phenyl-7%-methyl-86%-or OV-1701) was investigated as function of the cyclodextrin concentration. In order to study the effect of mixing, the data on the mixed stationary phases were compared with those obtained on pure OV-1701 and perpentylated β-CD and on coupled columns, individually coated with the pure phases. The validity of the retention model proposed in the literature by Schurig and co-workers was checked. Deviation from linearity was observed for some racemates. A possible explanation of the deviation is presented and a more general retention model on mixed cyclodextrin-polysiloxane phases is proposed.     

Intervalence electron transfer through a thiolate bridge ligand: a Fe–S–R–Fe mixed valence complex

The reaction of Cp(dppe)FeI with the ligands 2,2′- and 4,4′-dithiobispyridine (S₂(Py)₂) give the mononuclear or binuclear complexes of the type [Cp(dppe)Fe-S₂(Py)₂]PF₆, [Cp(dppe)Fe---SPy]PF₆ or [{Cp(dppe)Fe}₂-μ-SPy](PF₆)₂ depending on the reaction condition. Reaction of Cp(dppe)FeI with dithiobispyridines in presence of TlPF₆ as halide abstractor and using CH₂Cl₂ as a solvent gives the complexes [Cp(dppe)Fe-4,4′-S₂(Py)₂)₂]PF₆ (1) and [CpFe(dppe)-2,2′-S₂(Py)₂]PF₆ (2) whereas the same reaction using CH₃OH as a solvent and NH₄PF₆ as the halide abstractor leads to the formation of the Fe^III–thiolate complex [Cp(dppe)Fe-2,2′-SPy]PF₆ (3) and the mixed-valence complex [Cp(dppe)Fe^III-μSPy-Fe^II(dppe)Cp](PF₆)₂ (4). Magnetic and ESR measurements are in agreement with one unpaired electron delocalized between them. Mössbauer data indicate clearly the presence of two different iron sites, each one of the N-bonded and S-bonded iron atoms, with intermediate oxidation state Fe^II---Fe^III. An electron transfer intervalence absorption was observed for this complex at 780 nm (in CH₂Cl₂). By applying the Hush theory the intervalence parameters were obtained; =0.028, H_ab=361 cm⁻¹ which indicate Class II Robin–Day. Estimation of the rate electron transfer affords a value k_th=6.5×10⁶ s⁻¹. Solvent effect on the intervalence transition follow the Hush prediction for high dielectric constants solvents which permit the evaluation of the outer and inner-sphere reorganizational parameters, which were analyzed and discussed. The electronic interaction parameters compare well with those found for electron transfer in metalloproteins.