Teruzo Asahara

Novel reaction of phosphoranes with lactones. Formation and thermal ring closure of triphenyl(alkyl)phosphoniocarboxylate betaines

The reaction of alkylidenetriphenylphosphoranes with lactones affords triphenyl(alkyl)phosphoniocarboxylate betaines, which were thermally decomposed to give triphenylphosphine and lactones with the alkylidene groups of the starting phosphoranes introduced into the ring.

Present Situation on the Biodegradation Test Method of Nonionic Surfactants

The Biodegradation test method of anionic surfactants was established in 1967 and revised in 1968 as JIS K-3363. This method is only applicable to synthetic detergents primarily composed of alkyl benzene self onates, alkyl sulfate, alkyl polyoxyethylene ether sulfate, alkane sulf ovate and alkenyl self ovate. Establishment of the test method for nonionic surfactants was also desired at that time and is now under progress by the Biodegradation Sub-committee of the Society. This report covers present situation developed in the past two years in our sub-committee as interim report Biodegradation of several typical nonionic surfactants such as nonyl-phenol ethoxylate, lauryl alcohol ethoxylate, lauroyl di-ethanol amide, nonyl-phenol polypropylene ether as well as dodecene-1 derived LAS as a standard sample, was evaluated by physical and chemical analysis using shake culture and semi-continuous procedure. Test results indicate that polyoxyethylene group is degradable as shown by foam reduction, cobalt thiocyanate method and GLC observation of residue. This may suggest as long as foam pollution is concerned, nonionic surfactants such as nonyl-phenol ethoxylate are biodegradable. Further study is being conducted to elucidate pathways of degradation in connection with complete degradation.

Polymerization of Vinyl Monomer by Local Cell Mechanism and Formation of Polymer Film

It is well known that some molecular compound is formed by carbon tetrachloride and amine, and that the addition of the amine and copper to the telomerization system of carbon tetrachloride and vinyl compound affects the distribution of molecular weight of the telomers. The authors investigated the mechanism of dissolution of copper in carbon tetrachloride-amine system and applied this effect to the surface treatment of metals.A local cell was formed among copper, carbon tetrachloride, and an aliphatic amine. When copper was dissolved in the solution, an active chemical species was formed, by action of which vinyl monomer was polymerized. The rate determining step in the local cell was pesumed to be the cathodic reaction, in which the electron was transferred from copper to carbon tetrachloride-amine complex, and trichloromethyl radical was formed.

Cationic Telomerization of Isoprene with Phenyl Chloride

イソプレン (IP) と塩化プレニル (PC) とのカチオソテロメル化反応を行ない, 溶媒 ,触媒, 反応率, 反応試剤の比率等の変化によるテロマーの重合度や構造の変化を検討した。テロマーのうち, テローゲンとタクソーゲンの1対1付加物 (C10 テロマー) を蒸留で分離し, 加水分解したのち薄層クロマトグラフィーで同定した。その結果, ゲラニオール, リナロールが主生成物であることを確認した。触媒として, 塩化メチレン溶媒中では塩化第ニスズのアルコール付加物を, またエーテル中では塩化第二鉄を用いた。これらは反応の制御が容易で再現性も良い。生成テロマーの平均重合度は反応率の増加と共に増大するが, PC/IP 比にはそれほど影響されない。これは PC の重合およびテロマーの分枝に起因すると考えられた。

Formation of Whisker of Coated Polymer during Its Electrolytic Polymerization

The formation of whisker was observed during the electrolytic polymerization of acrylonitrile onto metal surface in the presence of styrene or benzene. It was found by X-ray analysis that the whisker was amorphous and some specific absorptions were evident in the region of lower wavelength of its IR spectrum. The molecular weight of polymer, or the component of the whisker, was about 1, 000.

Self-anionic Telomerization of Acrylonitrile on Aluminum Electrode Surface

The effect of solvents on self-anionic telomerization of acrylonitrile on aluminum electrode surface was studied during the course of studies on metal surface treatment by means of electrolytic polymerization processes. The results showed that the number of chain transfers was larger in the solvent of higher dielectric constant and the number was smaller with the stronger intensity of electric field.On the assumption that the chain transfer reaction is due to the hydride ion shift, it is shown that the solvent of high dielectric constant weakens the interaction between hydride ions and also the interaction between hydride ion and cathode; therefore, such a solvent can stabilize hydride ions.

Formation of Polymer Film onto Stainless Steel by Electrolysis of Methyl Methacrylate

The authors studied on the surface treatment of stainless steel for forming adherent film of polymer on the electrode with methyl methacrylate, of which the polymerization was initiated at the electrode. Formation of an efficient film was observed in the system of (methyl methacrylate-N, N-dimethyl formamide-sodium nitrate) for a defined time of electrolysis and current density. However, formation of a deliquescent film was observed under a certain condition. Probably, it would be caused by the deposition of supporting electrolyte as it was or as an different kind of salt. The time of electrolysis had effects on the structure of the film. A proper time of electrolysis was required for forming an efficient adherent film.The authors examined and failed in the formation of polymer film whith a different system of (dichloromethane-tetraethyl ammonium-p-toluene sulfonate-methyl methacrylate).

Self-anionic Telomerization of Acrylonitrile in Electrolytical Polymerization

During the surface treatment of metals by electrolytical polymerization, it was observed that the molecular weight of poly-acrylonitrile, which forms the adherent film, was decreased together with the increase in the number of its molecules in the presence of styrene. As the results of detailed investigation, it was confirmed that chain transfer reaction happened in the presence of styrene from reactive side of polymer to monomer. Then, the extent of the chain transfer was evaluated under many experimental conditions and also kinetic consideration was taken of these phenomena. It was further confirmed that the same chain transfer reaction as above also happened in the presence of benzene. It was presumed from these results that the chain transfer would be shifting of hydride, which was stabilized by benzene ring.

Studies on Aliphatic Polyesters. IV. The Synthesis and Properties of Polyglycolide-lactide

グリコール酸とD,L-乳酸との共重縮合によってポリグリコリド・ラクチドを得て,その構造および物性の検討を行なった。その結果,少量の乳酸添加が著しくポリグリコリド・ラクチドの分子量,極限粘度,密度,融点を低下することがわかり, この原因が第1,2および3報の結果から説明された。ポリグリコリド・ラクチドは乳酸含有率25%以下では結晶性で,含有率の増加とともに上記物性値の変化があると同時に,分子鎖間距離は増加し,25%以上で無定形物質となる。これらの検討の結果,ポリグリコリド・ラクチドはグリコール酸単位と乳酸単位が乱雑に配置した斜方晶系のジグザグ構造の線型ポリエステルであると推定された。

Statistical Considerations on the Results of Testing Methods of Film-Type Rust-Preventive Oils

SummaryThis report deals with statistical studies on the results of several tests for evaluating the preventive ability of film-type rust-preventive oils, such as humidity cabinet, salt-spray, artificial weathering, settle gelatine drop, contact angle test, etc. The relative merits of these tests were observed on their sensitivities derived from the minor data obtained by factorial experiments by the inductive statistical method. The sensitivity is defined as variance ratio in analysis of variance of factorial experiments. As the results of factorial experiments carried out by the same L8(27)—orthogonal array to which three factors of two levels and one factor of four levels were laid out it was found that the difference in information on the effects of factors is caused by the difference in sensitivity of each test, and it is essential to inquire into the sensitivities of these tests or to improve their characteristics for the purpose of statistical treatment.