Effect of Dissolved CO_2 and Tetrahydrofuran on the Polymerization of Acrylic Acid

Recently,c0mpressedgaseshavebeenusedins0megasantisolventprocesses,suchasfractionati0n0fnaturaIproducts,recrystallization0forganicandin0rganicmaterials,andpolymerpr0cessing'2.WestudiedtheeffectofthedissovledsupercriticaICO=andTHFonthep0lymerizati0n0fAA.Itwasn0tfoundintheliterature.ExperimentalOnemlacrylicacidmonomer,O.O20ginitiator2,2'-azobis(is0butyronitrile)(AlBN),anddesiredam0unt0fTHFwereaddedintoanopticalcelloflOml.CO,wascharged,stirreduntilvap0r-liquidequilibriumwasreachedatabout30…     

The Effect of the Chain Length on MMA Free Radicl Polymerization

It has been known that the propagation rate coefficient (kp) will change with monomer conversion, Friss, Hamielec et al.1-5 have proposed many formulas about kp to fit this change. In order to obtain the relation between Arrhenius parameters and monomer conversion, a group of kp values at the same monomer conversion must be measured. We adopted a new method through analysis of kp values measured by usual experimental techniques for this purpose. Firstly, we chose a value of monomer convers…     

Effect of the Charge and the Nature of Both Cations and Anions on the Solubility of Zwitterionic Amino Acids,Measurements and Modeling

The effect of the charge and the nature of both the cations and the anions of some electrolytic salts: sodium fluoride (NaF), potassium fluoride (KF), sodium bromide (NaBr), potassium bromide (KBr), sodium iodide (NaI), potassium iodide (KI), sodium sulfate (Na₂SO₄), potassium sulfate (K₂SO₄), calcium chloride (CaCl₂), and barium chloride (BaCl₂), on the solubility of zwitterionic amino acids (glycine, DL-alanine, DL-valine, and DL-serine) in aqueous solutions at 298.15 K are studied and discussed. A salting-in effect is observed for all amino acids under investigation with all electrolytes used in the present study, except for DL-alanine and DL-valine in aqueous solutions containing sodium fluoride where a salting-out effect was observed. The orders of the effect of the nature and the charge of both the anions and the cations are: F^- < Cl^- < Br^- < I^- < NO₃^- < SO₄^2-\mathrm{F}^{-}<{}\mathrm{Cl}^{-}<{}\mathrm{Br}^{-}<{}\mathrm{I}^{-}<\mathrm{NO}_{3}^{-}<{}\mathrm{SO}_{4}^{2-} with both sodium and potassium cations; Na⁺<K⁺<Ca²⁺<Ba²⁺ with chloride anion.     

Effect of Acetylene on the γ-Ray Crosslinking Polymerization of Various Kinds of Acrylic Monomers

The γ-radiation-induced crosslinking polymerization of methyl methacrylate (MMA), methacrylic acid (MAA), 2-hydroxyethyl methacrylate (HEMA), methyl acrylate (MA), and acrylic acid (AA) was carried out in bulk. The polymerization rates of AA and HEMA were much larger than those of other monomers. Acetylene had no influence on the polymerization rate in the initial stage, and the rate was dependent only on the kinds of monomers. In the absence of acetylene, gelation took place in PMA, PAA, and PHEMA obtained at complete conversion, but not in PMMA and PMAA. By the addition of acetylene, complete gelation of PMMA was observed, but no gel formation was observed for PMAA. Volume and weight swelling ratios were measured for PMA, PAA, PHEMA, and PMMA with complete gelation. It was found that by the addition of acetylene the molar concentration of crosslinks increased as much as about twice for PMA and PHEMA, and over about one hundred times for PMMA AND PAA. The relation between volume S_v and weight swelling ratio S_w was studied theoretically. S_v was expressed by the the equation, S_v = (p_p /p+)S_w+ (1 -p_p/p_s), as a function of S_w and the densities of pure polymer (p_p) and solvent (p_s) in swollen polymer.     

An Effect of the Nature of Immobilized Components on the Adsorption and Mass Transfer Properties of Ultrafiltration Membranes Based on Sulfonate-containing Сopolyamide

Russian Journal of Applied Chemistry - Ultrafiltration membranes based on aromatic copolyamide, comprising 10% of units with sulfonate groups were produced. The possibility of their use as a matrix...     

π-π interactions in the self-assembly of melamine and barbituric acid derivatives

Self-assembly of a pair of complementary molecular components, 5-(4-dodecyloxyben-zylidene)-(1H,3H)-2,4,6-pyrimidinetrione (PB12) and 4-amino-2,6-didodecylamino-1, 3, 5-triazine (M12) was studied by cyclic voltammogram, surface photovoltage spectroscopy, fluorescence spectroscopy, FTIR and X-ray diffraction. It is found that after mixing equimolar amount of PB12 and M12 at room temperature, not only triply complementary hydrogen bonds are formed between PB12 and M12 but also further self-assembly of the supermolecules based on network of hydrogen bonds occurs via π-π interactions. During the self-assembly of the supermolecules, π-π interactions are induced by delocalized interactions between the HOMO of M12 and the LUMO of PB12, resulting in the formation of a supramolecular nanotube with a layered structure bearing a d value of 0.41 nm and PB12 and M12are arranged alternatively between adjacent supermolecules.     

Influence of Cyclodextrin on the Styrene Polymerization

Cyclodextrin (CD) are oligosaccharides consisting of 6(α), 7(β), 8(γ) units of 1,4-linked glucose. Due to their polar hydrophilic outer shell and relatively hydrophobic cavity, they are able to build up host-guest complexes by inclusion of suitable hydrophobic molecules. The formation of these complexes leads to significant changes of the solubility and reactivity of the guest molecules, but without any chemical modification. Thus, water insoluble molecules may become completely water solu…     

π-π interactions in the self-assembly of melamine and barbituric acid derivatives

Self-assembly of a pair of complementary molecular components, 5-(4-dodecyloxyben-zylidene)-(1H,3H)-2, 4,6-pyrimidinetrione (PB₁₂)and 4-amino-2,6-didodecylamino-1, 3, 5-triazine (M₁₂) was studied by cyclic voltammogram, surface photovoltage spectroscopy, fluorescence spectroscopy, FTIR and X-ray diffraction. It is found that after mixing equimolar amount of PB₁₂ and M₁₂ at room temperature, not only triply complementary hydrogen bonds are formed between PB₁₂and M₁₂ but also further self-assembly of the supermolecules based on network of hydrogen bonds occurs via π-π interactions. During the self-assembly of the supermolecules, π -π interactions are induced by delocalized interactions between the HOMO of M₁₂ and the LUMO of PB₁₂, resulting in the formation of a supramolecular nanotube with a layered structure bearing a d value of 0.41 nm and PB₁₂ and M₁₂are arranged alternatively between adjacent supermolecules.     

On the Nature of the Cherdyntsev–Chalov Effect

It is shown that the Cherdyntsev–Chalov effect, usually presented as the separation of even isotopes of uranium upon their transition from the solid to the liquid phase, can include initiated acceleration of the radioactive decay of uranium-238 nuclei during the formation of cracks in geologically (seismic and volcanically) active zones of the Earth’s crust. The fissuring of the solid-phase medium leads to an increase in mechanical tensile stress and the emergence of strong local electric fields, resulting in the injection of chemical-scale high-energy electrons into the aqueous phase of the cracks. Under these conditions, the e^? catalytic decay of uranium-238 nucleus studied earlier can occur during the formation of metastable protactinium-238 nuclei with locally distorted nucleon structure, which subequently undergo β^–decay with the formation of thorium-234 and helium-4 nuclei as products of the fission of the initial uranium-238 nucleus with a characteristic period of several years. The observed increased activity of uranium-234 nuclei that form during the subsequent β-decay of thorium and then protactinium is associated with the initiated fission of uranium-238. The possibility is discussed of developing thermal power by using existing wastes from uranium production that contain uranium-238 to activate this isotope through the mechanochemical processing of these wastes in aqueous media with the formation of ₉₁ ²³⁸ Pa _isu , the half-life of which is several years.     

The Effect of Alkane Chain Length on the Liquid–Liquid Critical Temperatures of Oligostyrene/Linear-Alkane Mixtures

Summary. Upper critical solution temperatures (UCSTs) for liquid–liquid demixing in a set of mixtures of linear alkanes (pentane (N ₁=5) to pentacontane (N ₁=50)) with an oligostyrene (1241amu, N ₂=12) are reported. We find strong correlation between the Hildebrand solubility parameters of the alkanes and the UCST. Correlations are developed which enable predictions concerning the miscibility of mixtures of compounds with longer chains.     

The Effect of Alkane Chain Length on the Liquid–Liquid Critical Temperatures of Oligostyrene/Linear-Alkane Mixtures

Upper critical solution temperatures (UCSTs) for liquid–liquid demixing in a set of mixtures of linear alkanes (pentane (N ₁=5) to pentacontane (N ₁=50)) with an oligostyrene (1241amu, N ₂=12) are reported. We find strong correlation between the Hildebrand solubility parameters of the alkanes and the UCST. Correlations are developed which enable predictions concerning the miscibility of mixtures of compounds with longer chains.     

Effect of Polycondensation Reaction Conditions on the Properties of Thermotropic Liquid‐Crystalline Copolyester

In this study a range of wholly aromatic copolyesters based on kink m‐acetoxybenzoic acid (m‐ABA) monomer (33 mol%) and equimolar‐linear p‐acetoxybenzoic acid (p‐ABA), hydroquinone diacetate (HQDA) and terephthalic acid (TPA) monomers (67 mol%) have been synthesized by melt polycondensation reaction process at 280°C and 260°C for different time intervals. Characterization of copolyesters were performed by solution viscosity measurement, wide–angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), hot‐stage polarized light microscopy, proton‐nuclear magnetic resonance analysis (¹H‐NMR). According to the results obtained, copolyesters showed thermotropic liquid crystalline behavior in an appropriate temperature range. The copolyesters were prepared in high yields. It was observed that the intrinsic viscosities of the copolyesters are increased regularly with increasing polymerization time and temperature. All the copolyesters were soluble in a trifluoroacetic acid/dichloromethane (30:70 v/v) except the copolyesters which were synthesized at 280°C in 5 h. According to the WAXD results; the degree of crystallinity of copolyesters were found to be between 5–15%. DSC and hot stage polarized light microscopy results showed that all the copolyesters are melt processable and a significant molecular interaction exist in a very broad temperature range (160°C and 165°C) in the nematic mesophase. The T_g values are increased with an increasing polycondensation reaction time and temperature and they were observed between 93–126°C. Fibers prepared by a hand‐spinning technique from the polymer melt exhibit well‐developed fibrillar structure parallel to the fiber axis.     

Anionic Polymerization of α-Methylstyrene. IX. Nature of the Propagating Species

Abstract

The nature of the initiating and propagating species involved in the anionic polymerization of α-methylstyrene has been explored. The earlier hypothesis that multimodal GPC molecular weight distributions in polymers arise solely out of different reaction steps or different ion-pair mechanisms being involved has been modified for poly-α-methylstyrene. Multimodal GPC molecular weight distributions in poly-α-methylstyrene initiated with potassium at 25°C and polymerized at 25°C or higher in THF, p-dioxane, or cyclohexane as solvents have been ascribed to the presence of two different types of tetramers which grow simultaneously but at different rates, each responding to its own well-defined thermodynamic equilibrium and yielding dormant and living polymers. Reaction schemes describing the initiation (at 25°C) and propagation reactions (between -25 and 60°C) in the polymerization (in solution of THF as well as in bulk) of α-methylstyrene initiated with potassium-naphthalene, butyl-lithium, and butyllithium-tetramethylethylenediamine (TMEDA) have been presented. The role of coordinating agents naphthalene and TMEDA in changing irreversible propagations into reversible ones has been emphasized.     

π-Arene clusters of cobalt and ruthenium on the base of biphenyl

For the first time monocluster -arene derivatives of biphenyl Ph₂Co₄(CO)₉ and Ph₂Ru₆C(CO)₁₄, the shared mononuclear monocluster complex Ph₂Cr(CO)₃Co₄(CO)₉, and the bicluster derivative of cobalt Ph₂[Co₄(CO)₉]₂ have been synthesized. IR and H¹ NMR spectra of the compounds have been studied.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1978–1980, November, 1993.     

Effect of Ionic Liquid on Detection of Carbofuran by Plant-lipases Inactivation

Ionic liquids (ILs) as additive in phosphate buffer for detection of carbofuran by plant-lipases inhibition method is described. The higher inhibition efficiency and the shorter analysis time can be obtained by using N-butylpyridinium tetrafluoroborate ionic liquid-phosphate buffer mixtures instead of pure phosphate buffer.     

Effect of Oxygen and Bacteria on the Property of Polymer Gel

The viscosity property of Cr~(3 ),Al~(3 ),and compound ion cross-linked polymer gel solution in the anaerobic and aerobic environment was investigated aiming at meeting the practical demand of the oil field.The viscosity reserving effect after adding the biocide and the gelation in the anaerobic and aerobic environments was also studied in the paper.The results indicate that the viscosity of the cross-linked polymer gel solution caused by the water produced in aerobic environment is higher than that in anaerobic environment,and that the viscosity value of the cross-linked polymer gel solutions after adding biocides has improved to some extent and polymer gel has gelated well in anaerobic environment.     

Effect of the Nature of the Polymer Matrix on the Luminescence of Tb(III) Complexes with β-Diketone Copolymers

The formation conditions and luminescence of Tb(III) complexes with synthesized copolymers of unsaturated acetylacetone derivatives with styrene and methyl methacrylate were studied. The luminescence intensity of these Tb(III) complexes was found to depend on the β-diketone substituent nature (CH₃, CF₃, C₆H₅) and structure (linear, branched) and the β-diketone to monomer ratio in the polymerizing mixture.     

Effect of the Nature of the Template on Formation of the Spatial Structure of Germanium Dioxide under Sol–Gel Synthesis Conditions

We have synthesized for the first time novel forms of germanium dioxide, templated by micellar structures, with hexagonal and/or lamellar spatial structure. We used an original method for detemplating the synthesized materials. We show that it is possible to use these as the basis for obtaining mesophase sorbents, including mesoporous molecular sieves (MMSs). We note that in each specific case, in synthesis of new nanoperiodic and mesoporous materials, including semiconductors, the determining factor is the correct choice of certain template/framework former systems that match with respect to chemical structure and reactivity.     

Synthesis of Mixed Tail Triphenylene Discotic Liquid Crystals： Molecular Symmetry and Oxygen-Atom Effect on the Stabilization of Columnar Mesophases

Small change in chemical structure of discotic liquid crystals can cause big difference in their mesomorphism. Replacing of the alkoxy peripheral chains of triphenylene by oxygen-atom containing ester chains would result in novel mesomorphism. A series of mixed tail triphenylenes containing propoxyacetyloxy and alkoxy, abbreviated as C18H6（OCnH2n＋1）3（OCOCH2OC3H7）3, n=4-8, and hexa（propyloxyacetyloxy）triphenylene, C18H6（OCOCH2OC3H7）6 were synthesized. Thermal gravimetry analysis （TGA） of three discogens showed that they had good thermal stability till 350 ℃. The mesomorphism was investigated through differential scanning calorimetry （DSC） and polarized optical microscopy （POM）. The preliminary X-ray diffraction （XRD） results of one compound showed that it exhibited ordered hexagonal columnar （Colho） mesophase. These mixed tail triphenylene derivatives possessed much stable Colho mesophase and wider mesophase ranges than their hexaalkoxytriphenylene C18H6（OR）6 and hexaalkanoyloxytriphenylene C18H6（OCOR＇）6 analogues. The asymmetrical compounds 2,6,11-trialkoxy-3,7,10-tri（2-propyloxyacetyloxy）triphenylenes with n=5-8 displayed higher clearing points and wider temperature ranges than their symmetrical isomers 2,6,10-trialkoxy-3,7,11-tri（2-propyloxyacetyloxy）- triphenylenes, while C18H6（OCOCH2OC3H7）6 had the highest clearing point due to the β-oxygen-atom effect.