Effects of solvent in photo-induced graft copolymerization of vinyl monomers on cellulose

The effects of swelling of the sample and polymerization solvents were studied for photo-induced graft copolymerization of vinyl monomers on cellulose. The graft copolymerization of methyl methacrylate (MMA) was activated by swelling of the sample or organic solvent-water solutions within a certain range of their concentrations. Though each organic solvent gave a maximum in per cent grafting and the number of grafts at about 25 vol-% concentration, the initiation reaction scarcely took place at 100% concentration; thus, the solvent itself is considered to have a negative effect. The solvents used in the experiments were all hydrophilic, such as methanol, acetone, and dioxane. The average molecular weight of the grafted PMMA differed in each solvent, indicating a different characteristic effect of solvent on the growing grafted polymer radicals. The presence of ferric ion as a sensitizer stimulated further the contributions of the sample swelling and the organic solvents to the copolymerization reaction. A similar effect was observed for styrene as for MMA, but not for acrylic acid and methacrylic acid.     

On the theory of coagulation and the coalescence of mercury droplets in aqueous solutions

Summary The potential ranges of polarization of a pair of dropping mercury electrodes, over which the two mercury droplets coalesced, were measured as functions of ionic concentrations for various electrolytes. In the case of simple inorganic electrolytes the condition of coalescence obtained was proved to be in quantitative agreement with theVerwey-Overbeek theory of coagulation of lyophobic sols, thus indicating that the interaction between sub-microscopic particles of hydrophobic sols is essentially the same as that between macroscopic mercury droplets. While, in the case of sodium citrate solutions two kinds of marked deviations from the theory were observed, which appeared to be due to the specific adsorption of citrate ions and to the formation of protective interfacial films.

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Zusammenfassung Die Potentialbereiche der Polariation eines Paares von Quecksilber-Tropfelektroden, über die die beiden Quecksilbertropfen koaleszieren, werden als Funktion der Ionenkonzentration verschiedener Elektrolyte gemessen. Im Fall einfacher anorganischer Elektrolyte wurde die erhaltene Bedingung der Koaleszenz mit der Theorie vonVerwey-Overbeek der Kaogulation lyophober Sole geprüft und in quantitativer übereinstimmung befunden. Das zeigt, da\ die Wechselwirkung zwischen submikroskopischen Partikeln hydrophober Sole im wesentlichen dieselbe ist wie zwischen den makroskopischen Quecksilbertröpfchen. Dagegen ergaben sich im Fall von Natriumzitratlösungen zwei Arten markanter Abweichungen von der Theorie. Diese scheinen spezifische Adsorption der Zitrationen und die Ausbildung von SchutzgrenzflÄchenfilmen zur Ursache zu haben.

     

Studies of the polymerization of diallyl compounds. XXII. Polymerization of diallyl oxalate in the evolution of carbon dioxide at elevated temperatures

The polymerization of diallyl oxalate was conducted in the presence of radical initiators at a high temperature range of 80–180°C; a large decrease in degree of polymerization, an increase in residual unsaturation of the resulting polymer, and the evolution of carbon dioxide were observed with the elevation of temperature. These findings were reasonably interpreted by considering the dismutation of the uncyclized growing radical to yield the allyl radical, carbon dioxide, and polymer carrying a terminal double bond. The kinetics of the polymerization of diallyl oxalate in the evolution of carbon dioxide at elevated temperatures were also discussed in detail.     

Coating of borosilicate glass containers for preventing contamination in trace element analysis

Pyrex glass dishes are coated with amorphous 78 SiO₂—21 ZrO₂—1 Na₂0 (mol %) films ca. 50 nm thick. The coated dishes possess reasonable chemical resistance and can be successfully used in the dry ashing of a standard botanical sample for boron determinations and in the evaporation needed for aluminum determination in nitric acid.     

Further evidence for the intramolecular charge-transfer interaction between tropylium ion and remote benzene rings in 9,10-dihydro-9,10-(1,2-tropylio)anthracene tetrafluoroborate and its methyl derivatives

A series of 9,10-dihydro-9,10-(1,2-tropylio)anthracene tetrafluoroborates

has been prepared. The intramolecular charge-transfer interactions in

were confirmed by their UV spectra and pK_R+ values. As a model compound 1,2,3,4-tetrahydro-1,4-(1,2-tropylio)naphthalene tetrafluoroborate ($\text{5}$)_was also examined.     

Steady-state and nanosecond spectroscopic studies of triplet sensitized reaction of K-region arene oxides

Photorearrangement reactions of K-region arene oxides, 9,10-epoxy-9,10-dihydrophenanthrene (1a), 3-acetyl-9,10-epoxy-9,10-dihydrophenanthrene (1b), and 3,4-epoxy-3,4-dihydropyrene (1c) in dichloroethane (DCE) solution were investigated by steady irradiation and nanosecond transient spectroscopy. Photorearrangements producing substituted oxepins, 2 occur via the singlet excited state of these compounds, while the phenolic products, 9-hydroxyphenanthrene (3a), 3-acetyl-9-hydroxyphenanthrene (3b), and 4-hydroxypyrene (3c) are formed via the triplet state. Phenol 3 formation from the triplet 1 sensitized by the triplet 3 (i.e. product sensitization) is proposed for the photorearrangement reactions of 1a and 1c, and this process is the only way phenol (3a) is formed because of the negligible intersystem crossing probability of 1a. No product sensitization occurs in the photorearrangement reaction of 1b.     

Studies on furan derivatives. XII. Nucleophilic substitution of methyl 5-nitro-2-furancarboxylate. Preparation of methyl 5-phenoxy-2-furancarboxylates

Twenty one methyl 5-phenoxy-2-furancarboxylates prepared from the reaction of methyl 5-nitro-2-furan-carboxylate with phenoxides via displacement of the nitro group. In the reaction of potassium 2-nitrophen-oxide with methyl 5-nitro-2-furancarboxylate at 110°-120°, 2,2′-dinitrodiphenyl ether was obtained as a main product.