kogyo kagaku zasshi - j-stage

Kogyo Kagaku Zasshi

( Journal of thn Chemical Society of Japan, Industrial Chemistry Section)

Vol. 74, No. 2, pp. 137-320 (1971)

Abstracts

These abstracts are prepared for the benefit of our readers abroad in order to assist them to get a general idea of the contents of the preseut issue, written in Japanese by the respective authors. Readers are recommended to refer to the figures, tables, formulae etc. from the original papers. Editor

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ORIGINALSIn the above study values of K1 and K2 obtained 2.13±0.03 and 0.408 + 0.005 respectively. Both spectra of FeBr2+ and

Kogyo Kagaku Zasshi 74, 137---s142 (1971)

Fatigue of Photochromic Materials of Spiropyran

by Mitsunobu NAKAZAWA, Kaneki YOSHIDA, Hiroshi KOKADO and Eiichi INOUE

The decrease of attainable color density of photochromic materials is known as the fatigue of the materials. The fatigue has been studied with photochromic spiropyran in polymer film and solution. The fatigue was strengthened when the materials were imposed upon the repeated photo-coloration-decoloration cycles, compared to when they were Continuosly irradiated. Observations of the spectral change, the temperature effect and the above mentioned repetition effect upon the fatigue, indicate that the fatigue arises through two photo-processes; one from the colorless species and the other from the colored species, and the former process is predominant. More fatigue arose at less inter-molecular distance of spiropyran molecules in solutions. The result suggests that the fatigue is caused by interac- tion between spirapyran molecules. The fatigue in polymer filmes depended remarkably on residual solvent in films, and also on temperature, spiropyran concentration and the polarity of polymer. More fatigue was observed in oxygen-free solutions.

Imaging Science and Engineering Laboratory, Tokyo Institute of Technorogy : Ookayama, Meguro-ku, Tokyo, Japan

Kogyo Kagaku Zasshi 74, 142-.'147 (1971)

Formation of Complex Iron(111) Ions with Bromide Ions in

Aqueous Solutions*

by Kiichi TERUYA, Toshio SEKI and Issei NAKAMORI**

The fomation of FeBr2+•- and FeBr2+-complexes, at the first and second step of the consecutive reaction of ferric ions with bromide ions, has been studied spectrophotometri-cally in aqueous solutions.

The association constants and the molar extinction coef-ficients of each complex were determined at wave length in the range of 380,-450 mit, ionic strength of 3 .0 and at 20°C.

FeBr2+ showed maxima in the neighborhood of 407 mg and EFeBr2+ (407 mu) = 216, eFeBr2+ (407 m,u) = 930 were obtained.

From the change of association constants, the following were calculated at 20°C : for FeBr2+-complex; K10=4.75 ,

4G10= —0.91 kcal/mol, 4H1° =6.10 kcal/mol, Z1S1°:---- 17.7 e. u., and for FeBr2+-complex; K20= 0.98, 4G20=0.001 kcal/mol, AH20

= 2.74 kcal/mol, 4S20=9.34 e . u.

* A Study on Separation Processes with Formation of Complexes.

*. Department of Chemical Engineering , Faculty of Engineering, University of Kyusyu: Hakozaki, Fukuoka, Japan

Kogyo Kagaku Zasshi 74, 147,--,152 (1971)

Influence of Dopents on Decomposition Reaction of

Cobalt-Cobaltic Oxide*

by Hiroshi 1CHIMURA and Wazo KOMATSU**

The influence of dopents (Li20, Na20, Al203, and In203) on the decomposition reaction of Co304 was studied isother-mally in the temperature range of 700°C to 800°C in vacuum

(5 x 10-3 torr.). Automatic recording thermogravimetic balance was used to measure the change in weight due to

gas evolution as a function of time. The kinetic data for pure Co304, Al doped, and In doped oxide were described by interfacial model, and for the Li doped and Na doped oxide showed induction period in the initial stage of reaction . The induction period was ascribed to the slow nucleation of Co0 observed with an electron microscope in the stage. The activation energy for the decomposition of pure Co304 was 87.7 kcal/mol, and in agreement with the value of reaction enthalpy obtained by the measurement of the decom-

position pressure of pure Co304. Polanyi-Wigner model could explain the initial velocity of reaction.

* Studies on Reaction of Co3043Co0+1/202. I. ** Faculty of Engineering , Tokyo Institute of Technology :

Ookayama, Meguro-ku, Tokyo, Japan

A 16 Kogyo Kagaku Zasshi

Kogyo Kagaku Zasshi 74, 152,-,155 (1971)

Moisture Absorption Process of Powder Particles of

Some Water-Soluble Chlorides

by Takafumi KANAZAWA, Mamoru KAIHO and Masatoshi CHIKAZAWA

In regard to hygroscopicity of powder particles of sodium, ammonium and potassium chlorides, relation between the moisture content and the water vapor pressure, and change of the moisture absorbing rate at the initial stage during a hygroscopic process have been investigated.

With increasing moisture content in the three samples, the water vapor pressure in equilibrium with the absorbed water rose quickly at the initial stage, then kept up a value of the saturated aqueous solution of the salt. On the other hand the hygroscopic rate kept up a fixed value till all the

particles liquefied except for the depression at the beginning. The above results showed within the present experiments

that when the moisture content increased the effective surface area for absorbing water vapor decreased quickly

in the initial period and then the slight and linear decrease was followed by a fixed value. It was also deduced that the volume of solution film formed by the moisture absorp-tion on the surface of a particle required 1,000-6,000 A in thickness to show a value of the water vapor pressure of the saturated solution.

Department of Industrial Chemistry, Faculty of Technology, Tokyo Metropolitan University: Fukazawa, Setagaya-ku, Tokyo, japan

Kogyo Kagaku Zasshi 74, 155,—,159 (1971)

Thermal Decomposition and Fluorine Volatility in the Systems Fluorapatite-Reactants

by Takafumi KANAZAWA, Hideki MONMA

and Seiichi ISHII

Thermal reactivities of silica, aluminum phosphate, some chlorides and hydroxides with synthetic fluorapatite prepared by a dry process have been investigated by using DTA, X-ray diffraction and fluorine analysis.

Addition of silica or silica gel to the apatite increased markedly the volatility of fluorine on heating in water vapor atmosphere. A1PO4 decomposed the apatite to form ,3- Ca3(PO4)2. This reaction proceeded rapidly above 1,150°C; a high reactivity was observed in a stream of air. No effect of Mg(OH)2 on the apatite was recognized under this heating condition. LiOH decomposed the apatite above 450°C to form Li3PO4 and CaO, whereas less fluorine was volati-lized. The reaction of CaCl2 formed a product composed of

Ca2PO4C1 or Ca10(PO4)6(C1, F)2. MgCl2 gave the same com-

pounds as did CaCl2 when treated in the air, while in nitrogen gas stream (200 m//mm), Ca2PO4C1, Mg3(PO4)2 and an uncertain compound in the system MgO—P205—MgF2 formed. Both additives, MgC12 and CaCl2, resulted in a slight volatilization of fluorine. It was found that in gaseous SiC14 stream fluorine volatilized remarkably and that both silicon and chlorine were fixed in the calcined products to form a-cristobalite, CaCl2, Ca10(PO4)6(C1, F)2 and Ca2P207.

Department of Industrial Chemistry, Faculty of Technology, Tokyo Metropolitan University : Fukazawa, Setagaya-ku, Tokyo, Japan

Vol. 74, No. 2 (1971)

Kogyo Kagaku Zasshi 74, 160,---,163 (1971)

Trimethylsilylation of Calcium Silicate

by Kali KOMATSU, Itiro TO YAMA,

Akinori KAWAHARA and Tomizo NAKAMURA

The purpose of the present investigation is to establish the condition of the hydrothermal synthesis of calcium silicate which is used as noninflammable construction ma-terial, and to develop the application of silicate inorganic

polymer. The Lentz method of preparation of trimethylsilylation were applied to several kinds of calcium polysilicates, and thrre types of trimethylsilyl derivatives were derived and separated into following species ; insoluble three dimensional block, soluble volatile fraction having single linear chain and soluble non-volatile fraction having ladder chain struc-ture, and the latter two were analysed with the molecular weight and IR spectrum. From the results, it was found that molecular weight of the obtained polysilicate was smaller from the starting material which was prepared by the low temperature and short time reaction conditions than that by the higher and longer ones. Therefore, is was concluded that probably the condensation and propagation reactions of the siloxane linkages proceeded during the hydrothermal synthesis of the calcium silicate. Another interesting result found was that the siloxane linkage Si-0-Si found in Al-bearing tobermorite was intersected by aluminoxane bond -A1-0- by the ratio of Si : Al= 5-6 : 1.

Government Industrial Research Institute Osaka : Midorigaoka, Ikeda, Osaka, Japan


Non-destructive Determination of Fluorine with Be-D

Neutron Activation Analysis Using Gold as Internal Standard*

by Kiyokatsu JINNO, Mamoru YOSHIKAWA and Daido ISHII**

A rapid and non-destructive method was required for the

determination of the fluorine content of various com-

pounds. The time-consuming nature of conventional ana-lytical techniques led to the investigation of fast neutron activation analysis for the determination of fluorine. In the

present paper, the method for the determination of fluorine based on the short half-life isotopes '6N, produced by the reaction 19F(n, a)16N was investigated. The advantage of utilizing this reaction is due to the high energy of the

gamma-radiation which enables most interferences to be eliminated. Interferences due to the reaction 160(n,p)16N can be avoided by using Be-D neutrons of energy below the threshold for the (n, p) reaction on NO.

To avoid the lowering in precision due to change in the analytical condition, especially neutron flux, gold was used as an internal standard material. Since 167mAu produced by the reaction 197Au(n, n,)197mAu has similar half-life to 16N, the activity of the latter is conveniently normalized by that of the former.

As a result, a straight line was obtained as the calibra-tion curve for the fluorine determination wih relative mean error of 2.10 for 60 to 800 mg of fluorine.

Kogyo Kagaku Zasshi

This method is useful as an analytical procedure for

fluorine determination by fast neutron activation analysis.

* Activation Analysis with Be -D Neutrons . II. ** Department of Applied Chemistry , Faculty of Engineering,

Nagoya University : Nagoya, Japan

Kogyo Kagaku Zasshi 74, 167—'170 (1971)

Fluorine Combustion Gas Chromatography— A New Method for Elemental Analysis*

by Katsuichi ASAI and Daido ISHII**

A fluorine combustion gas chromatographic method was

proposed in organic elemental analysis. In this method the sample is burned in an atmosphere of excess fluorine, then the determination of the products is carried out by gas chromatography. A commercial gas chromatograph had to modified to analyze the corrosive products burned with fluorine successfully. Therfore, nickel and teflon were used for all the tubing carrying gases.

Fluorine was prepared by a devised generator using the molten potassium bifluoride as electrolyte. This apparatus is a handy fluorine generator and can be used in a laboratory. In this apparatus the evolution rate of fluorine gas can be adjusted by changing electrolytic voltage. A special vessel was made of the monel alloy to burn the sample in excess fluorine. This vessel has an attachment through which the liquid samples can be injected.

Using this apparatus, organic samples (n-C61-114, C6H6, CH2C12, CHC13) were analyzed. Combustion products (CF4, HF, C12) were determined by the gas chromatograph using the polytrifluoroethylene oil as a stationary liquid phase of the column and helium as a carrier gas.

Consequently, this procedure was found to be useful for a new analytical method in elemental analysis. This method has advantage that simultaneous analysis of many elements is possible and there is no necessity to weigh the sample. Furthrmore, micro analysis is possible since the detector has high sensitivety.

* Study of the Elemental Analysis with Fluorine Combusion Gas Chromatography. I.

** Institute of Techno-Analytical Chemistry, Faculty of Engineering, Nagoya University : Chikusa-ku, Nagoya, Japan

Kogyo Kagaku Zasshi 74, 171'-.'178 (1971)

Substituent Effects on the Hydrogen Bonding of

Urethanes*

by Takehide TANAKA**, Tetsuo YOKOYAMA**,

Yukio YAMAGUCHI**, Seikou NAGANUMA*** and Mutsuhisa FURUKAWA****

Substituent effects on the hydrogen bonding of urethanes

(R-NHCOO-R') have been studied by IR spectroscopy. Molar absorption coefficients of free N-H stretching vibrations were determined to be about 200 //mol-cm for N-aromatic sub-stituted urethanes, about 120 l/mol-cm for N-aliphatic and alicyclic substituted urethanes. The frequencies of N-H and

C.0 stretching vibrations (NH and vc,.0) decreased with the increase of inductive effect of N-substituents and 0-substi-tuents, respectively. Hydrogen bonding per cents of sub-stituted urethanes in different concentrations were calculated. The N-aromatic substituted urethanes gave larger hydrogen

Vol. 74, No. 2 (1971) All

bonding per cents than N-aliphatic ones. The N- and 0-

aliphatic substituted urethanes showed maximum hydrogen

bonding per cents at an inductive index value. This pheno-

menon was explained as due to the inductive and steric

effects of substituents, which contribute in opposite direc-

tions.

* Studies on Polyurethanes . XV. ** Department of Applied Chemistry , Faculty of Engineering,

Kyushu University : Hakozaki, Fukuoka, Japan *** Mitsui Petrochemical Industries , Ltd. , Ohtake Branch:

Ohtake, Hiroshima, Japan **** Idemitsu Chemical Industries , Ltd. , Tokuyama Branch:

Tokuyama, Yamaguchi, Japan

Kogyo Kagaku Zasshi 74, 179,-s182 (1991)

Effect of Several Factors on Liquid Phase Oxidation of

Ethylene with Palladium Chloride-Active Charcoal Catalyst*

by Kaoru FUJIMOTO, Osamu KUCHIISHI and Taiseki KUNUGI**

Liquid phase oxidation of ethylene with palladium chloride-active charcoal catalyst was studied with respect to several factors affecting the yield of acetaldehyde.

Similar to the case of homogeneous catalyst system the reaction was suppressed by hydrochloric acid. The over-all activation energy was about 10 kcal/mol. Maximum selectivity of acetaldehyde (980) was obtained at tempera-tures 80-90°C. Maximum reaction rate was obtained when mole ratio of etylene to oxygen was 4 : 1.

Carbon dioxide, and small amounts of butenes and ethyl-chloride were by-products.

Oxygen suppressed the reaction while ethylene promoted it but the formation of carbon dioxide was promoted by

oxygen. The reason for the suppression due to oxygen was ambiguous.

* Oxidation of Olefins over Metallic Salts Active Charcoal Catalysts. VI.

** Department of Synthetic Chemistry, Faculty of Engineering, Universily of Tokyo : Hongo, Bunkyo-ku, Tokyo, Japan

Kogyo Kagaku Zasshi 74, 183,--"186 (1991)

Production of Furan by Vapor-phase Catalytic Oxidation

of Butadiene*

by Mamoru Al**

The direct vapor-phase catalytic oxidation of butadiene to furan has been investigated in order to determine the effect of catalysts and reaction variables on the yield of furan.

From the research on such molybdenum-type catalysts as V-Mo-P, Mo, Mo-P, Mo-Bi, Mo-Bi-P, it was found that the best results for furan formation were obtained with Mo-P catalyst. It was also found that in the Mo-P system, the highest oxidation activity and furan formation were obtained in the region P/Mo=0.1—d0.2. The effect of such reaction variable as oxygen concentration, total gas flow, addition of the yield of furan were also studied.

* Study on Partial Catalytic Oxidation of Hydrocarbons . VIII. ** Research Laboratory of Resources Utilization, Tokyo Institute of

Technology : Ookayama, Meguro-ku, Tokyo, Japan

Al2 Kogyo Kagaku Zasshi

Kogyo Kagaku Zasshi 74, 187-191 (1971)

Co-oxidation of Crotonaldehyde with Propylene*

by Yasuaki MAEDA, Mamoru Al and Sadao SUZUKI**

Co-oxidation of aldehydes with propylene at room tempera-ture in liquid phase were studied. Oxidation of aldehydes was retarded by propylene. Measuring these retardations the reactivies of acylperoxy-radicals with propylene were assumed to be in the order of acetaldehyde>propionaldehyde

> n-butyraldehyde > crotonaldehyde. At low temperature only the co-oxidation of crotonaldehyde with propylene formed propylene oxide. The formation path of propylene oxide is the reaction of formed peracid with propylene. The rate equation of oxidation of crotonaldehyde is

V k(RII0)312(02)1/2 and the apparent activation energy is 20.1 kcal/mol. The rate equation of the epoxidation of percrotonic acid with

propylene is v' = F(RCOOOH)(Propylene)

The apparent activation energy is 11 kcal/mol.

* Co-oxidation of Olefin with Aldehydes. I. ** Research Laboratory of Resources Utilization, Tokyo Institute of

Technology: Ookayama, Meguro-ku, Tokyo, Japan

................................... ...... ............. ..............


Dehydrogenation of Isobutylaldehyde

by Michiya OHTSUKA, Yukio KIKUCHI and Tsuneo IKAWA

Dehydrogenation of isobutylaldehyde (IBA) was studied, to obtain methacrolein (MA) in a high selectivity, on various oxides in the temperature range of 350—,450°C using a flow reactor. The results showed that oxides of Bi-P (atomic ratio : 2/1) and Bi-Sb (atomic ratio : 1/1, 1/2) gave the best selectivity of 95 mol of reacted IBA to MA. Inactive oxide after the reaction was regenerated by heating with oxygen, but the addition of oxygen in a reactant gave a large amounts of combustion products. Some experimental results indicated that the oxygen in lattice of oxide con-tributed to the dehydrogenation of IBA.

Faculty of Engineering, Tokyo Institute of Technology: Ookayama, Meguro-ku, Tokyo, Japan

Kogyo Kagaku Zasshi 74, 196,----'199 (1971)

Desulfurization of Heavy Oil by Hydrogenation with Molybdenum-Nickel-Alumina Catalyst

by Toshio ISHIKAWA, Kazuo SHIMADA, Takashi HAYAKAWA, Katsuomi TAKEHIRA,

Satoshi OHSHIMA, Yasunori KURIKI and Yoshihide KOTERA

Hydrodesulfurization of heavy oil (containing 4.26 wt of sulfur) with Mo-Ni-Al203 catalyst prepared from ammonium

paramolybdate, nickel nitrate and alumina hydrate was studied. The desulfurization reaction was carried out in the temperature range of 360,400°C under a hydrogen pres-sure of 100 kg/cm2.

The catalyst containing Mo and Ni components on Al203 were more active than one component catalyst, Mo-Al203 or Ni-Al203.

The Mo-Ni-Al203 catalyst containing 0.05 g atoms of Mo and 0.034 g atoms of Ni in 100 g-catalyst showed the desul-

Vol. 74, No. 2 (1971)

furization activity of 63.46/,when the reaction proceeded under the condition of 4 of WHSV (space velocity of feed oil in weight/hr • weight-catalyst) at the aeaction tempera-ture of 400°C. The activation energy of this reaction was estimated to be 17 kcal/g atom-S.

It is observed that the desulfurization activity would be caused by the amorphous structure formed by the combina-tion of Mo and Ni-oxides with amorphous y-Al203.

Government Chemical IndustrialResearch Institute, Tokyo: Hon-machi, Shibuya-ku, Tokyo, Japan

Kogyo Kagaku Zasshi 74, 199---203 (1971)

Catalytic Dehydrochlorinations of 3,4-Dichloro-1-

butene and 1,2-Dichloropropane

by Hiroo TOMINAGA, Tadashi NAKAMURA,

Hiromichi ARAI and Taiseki KUNUGI

In a fixed-bed flow reactor, catalytic reactions of 3,4- dichloro-1-butene, 1,4-dichloro-2-butene, and 1,2-dichloro-

propane were investigated over silica alumina, alumina gel, silica gel, magnesium oxide, calcium oxide, and sodium or potassium hydroxide (solid or supported on silica gel) at

150,--,250°C. The following reaction pathways were found to be predominant:

CI

Cl CI 13,--'rC=C-C=C Cl A

C-C-C=C C-C=C-C A

AC1

C=C-C=C B : basic catalyst (NaOH, KOH)

A : acidic catalyst (the others of the catalysts tested) From stereospecificity observed in the dehydrochlorination

of 1,2-dichloropropane, E2 or ElcB mechanism was suggested for acidic or basic catalysts, respectively.

Department of Synthetic Chemistry, Faculty of Engineering, University of Tokyo : Hongo, Bunkyo-ku, Tokyo, Japan

Kogyo Kagaku Zasshi 74, 203—s207 (1971)

Synthesis of 1,2-Dimethoxyethane from Ethylene

Dichloride*

by Takashi KOYANO, Katsumi KANEKO, Masato KOMATSU and Seiji USAMI**

Synthesis of 1,2-dimethoxyethane by methanolysis of ethy-lene dichloride was investigated. Weakly basic materials such as magnesium hydroxide or zinc hydroxide are neces-sary to be present in the reaction system as the absorbent of evolving hydrogen chloride. Generally the addition of solvents which lower the polarity of the solution retards the reaction. The reaction occurs mostly in the liquid

phase and the optimum temperature appears to be 200°C. The reaction proceeds as successive pseudo 1st order reac-tions, in which the rate of the second step is larger than that of the first one. Preparation of 1,2-dimethoxyethane is possible with more than 800 selectivity for more than

850' conversion of ethylene dichloride.

* Syntheses of Glycol Ethers . I. ** Central Research Laboratory, Toa Nenryo Kogyo Co. : Oi-machi.

Iruma-gun, Saitama, Japan

Kogyo Kagaku Zasshi

Kogyo Kagaku Zasshi 74, 2D7-,210 (1971)

Synthesis of 1,2-Dimethoxyethane from Ethylene by

Iodine Catalyst*

by Takashi KOYANO, Osamu WATANABE

and Masato KOMATSU**

When ethylene is allowed to react with iodine in methanol

at 100-160°C, 1,2-dimethoxyethane is formed, and the

presence of oxygen makes the reaction catalytic by regene-rating iodine. The reaction consists of competitive formation

of 1,2-diiodoethane and 1-iodo-2-methoxyethane, followed

by methanolysis. The hydrogen iodide evolved should be

removed immediately by oxidation since it cleaves the ether

linkage of 1,2-dimethoxyethane and reacts preferentially

with methanol to give methyl iodide under the reaction

conditions. Dissolution of oxygen into the reaction solution

is rate determining for the oxidation of hydrogen iodide.

These reactions were investigated kinetically.

* Syntheses of Glycol Ethers . II. ** Central Research Laboratory , Toa Nenryo Kogyo Co. : Oi-machi,


Kogyo Kagaku Zasshi 74, 211 ---d214 (1971)

Synthesis of 1,2-Dialkoxyethane from Ethylene by

Copper Chloride Catalyst*

by Takashi KOYANO, Katsumi KANEKO

and Osamu WATANABE**

Chlorination of ethylene with cupric chloride has been carried out in methanol in the presence of oxygen. The total yield of 1,2-dichloroethane and 1-chloro-2-methoxy-ethane(CME) on the basis of reacted cupric chloride was more than 100$, showing the regeneration of cupric ion by oxidation of cuprous ion. The rate of oxidation of cuprous chloride is proportional to the concentration of oxygen in the reaction solution. Similar catalytic reaction is possible when cuprous chloride and hydrogen chloride are used as the chlorinating agent instead of cupric chloride.

Synthesis of 1-alkoxy-2-methoxyethane by the reaction of CME with alkali alkoxide was studied. For example, the reaction of CME with sodium methoxide at 100°C yielded

1,2-dimethoxyethane in ca. 90$ selectivity. The rate of substitution reaction is the largest for ethoxide among alkoxides of various carbon numbers, and the rate of elimination reaction increases with the branching. The rate of reaction is also influenced by the counter cation, and the rates increase in the order of K>Na>Li. The rate constants were calculated by the assumption that the reactions proceed by both free ion and ion pair.

* Syntheses of Glycol Ethers . III. ** Central Research Laboratory , Toa Nenryo Kogyo Co. : Oi-machi,


Kogyo Kagaku Zasshi 74, 215---,218 (1971)

Condensation of Crotonaldehyde in Vapor Phase

by Eitaro MORITA and Yasuhisa MATSUI

The condensation of CH3CH : CHCHO (.I ) to aromatic com-pounds in the presence of soda lime and Ca(OH)2 was studied. The vapor of ( I ) was diluted with N2 to about

50$ and passed on soda lime or on Ca (OH)2 at several temperatures. The products were analyzed by gas chromato-

Vol. 74, No. 2 (1971) A13

graphy using polyethylene glycol column. In the case of soda lime the condensation occurred around 220°C. At 220°C the yield of o-CH3C6H4CH0(10 was 17.4$ of ( I ), while the yield of the hydrogenated product of (n), o-CH3C6H4CH2.

OH (I11) was 16.20. The yield of each of the other side reaction products, CH3(CH2)2CHO (iv) and CH3(CH2)2CH2OH

(V) was 1-20 of ( ). In the case of Ca (011)2 the con-densation took place at around 300°C and the yield of (To was 2400 of ( ). The yield of each of the other side reaction products (Ill), ONO (v) and p-CH3C6114CHO was

160 of ( ). Presumably the peak of 1,3-cyclooctadiene was newly found on the chromatogram of the reaction product at 330°C.

Kyushu Institute of Technology : Sensui, Tobata-ku,

Kitakyushu-shi, Japan

Kogyo Kagaku Zasshi 74, 218—'220 {1 971)

Dependence of Solution Structure on Temperature in

the Concentrated Solution Forming the Reversed

Micelle of Nonionic Surface Active Agents*

by Shigetaka KUROIWA, Hideomi MATSUDA

and Katsutoshi MASADA**

In order to investigate the change of solution structure of nonionic surface active agents with temperature in the concentrated solution in which reversed micelle is formed, the temperature dependence of flow birefringence and vis-cosity were examined in the temperature range of 10° to 80°C for 80-950 aqueous solutions of two polyoxyethylene nonylphenylethers, whose polyoxyethylene group have poly-merization degrees of 12 and 8.5, respectively. With a solution concentration >85$ in the former and >90$ in the latter, the negative values of birefringence increased with the increasing temperature and reached zero above a definite temperature and further elevation of temperature made birefringence of these solutions negative again. The temperatures, from which these solutions commenced to show negative birefringence again, agreed with those at which their viscosities had minimum values. Based on these experimental results, the change of solution structure with temperature in 80-95$ solutions of nonionic surface active agents was discussed, and an attempt was made to have the diagrams illustrating the solution structures.

* Colloidal Studies on Textile Agents . XX. ** Faculty of Textile , Shinshu University : Tokiiri, Ueda-shi, Japan

Kogyo Kagaku Zasshi 74, 220223 (1971)

Quaternarization of Isoxazolidine and Properties of

Its Quaternary Salts

by Isao IKEDA, Go TAKEMOTO and Saburo KOMORI

The object of this report is to clarify the properties and reactivities of isoxazolidines containing long alkyl group,

which were synthesized by addition of a-phenyl-N-methyl-nitrone. The possibility of a formation of quaternary salts and their properties were studied.

2 - Methyl - 3 - phenyl - 5 - dodecylisoxazolidine was stable enough to be recovered after heating in 10% sodium hy-droxide aqueous solution or 10$ hydrochloric acid. Neither hydrochloride nor picrate of isoxazolidine could be isolated, but the quaternarization occurred with methyl chloride or bezyl chloride. The rate of quaternarization of isoxazolidine

A14 Kogyo Kagaku Zasshi

was slower than that of dimethyllaurylamine. Quaternary

products were white and very hygroscopic leaflets.

Quaternary salts have a large effect to stop the growth

of bacteria. Thus, 2,2-dimethyl-3-phenyl-5-dodecylisooxa-

zolidinium chloride was effective toward Staphylococcus

aureus 209P at 400,000 fold dilution.

Differential thermal analysis of the salt crystal was carried

out and surface tention of aqueous solution of the salts

was measured.

Department of Applied Chemistry, Faculty of Engineering, Osaka University : Yamadakami, Suita, Osaka, Japan

Kogyo Kagaku Zasshi 74, 224,--'227 (1971)

Separation of Each Component of Condensation Product

between Benzyl Chioride and Sodium Sulfanilate

and Their Surface Active Properties

by Kenji NEGORO and Kenichi SAIDA

Each component of Solution Salt B, sulfanilic acid (S), monobenzylsulfanilic acid (MB) and dibenzylsulfanilic acid

(DB) was separated. Surface tension, viscosity, and electro-conductivity as well as ability of solubilization, emulsification and permeation were measured for the aqueous solutions of these components. The results obtained were as follows.

1) Diminution of surface tension and the ability of solubilization of Orange OT into water were remarkable in DB. 2) A linear relation was observed between equivalent

conductivity and root of concentration of the aqueous DB solution brake at 0.5 g/100 ml.

3) The curves of surface tension'-'log c (c : concentra-

tion) , equivalent conductivity— A/ c and amount of the solu-bilized Oranged OT-sc showed the break at almost the same concentration and this was considered as critial concentra-tion for micelle formation.

4) The emulsification of liquid paraffin in water and the

permeation of water into felt were observed only in DB. 5) The order of surface tension lowering of the mixed

aqueous solutions of S, MB and DB was comparable to that of pure sample of DB.

6) The effect of pH upon surface tension of the aqueous solution was little in MB, while maximum of surface tension was observed at isoelectric point (pH 6.7) of DB.

From these results, it is concluded that DB is a better surfactant than MB regarded as a chief component in

Solution Salt B.

Department of Applied Chemistry, Faculty of Engineering,

Hiroshima University: Sendamachi, Hiroshima-shi, Japan


Synthesis of p-Substituted Styrene from p-Substituted

Benzylchloride and Dimethylsulfonium Methylide

by Zen-ichi YOSHIDA and Eijiro NISHI

Dimethylsulfonium methylide has been found to react with p-substituted benzylchloride in presence of t-butoxide in dimethyl sulfonium oxide to give a corresponding p-substituted styrene. Within the range of a not so large electronic effect of the substituent, the formation of p-substituted styrene has been easier with higher electron-donating property of the p-substituent. However the com-

Vol. 74, No. 2 (1971)

petitive formation of p,p'-disubstituted styrene has become easier to take place as the electron-withdrawing property

of the p-substituent becomes stronger. Especially, the latter

reaction has almost quantitatively occurred for p-nitro

derivative.

On the other hand, for p-methoxy benzylchloride having

strong electron-donating group, p-substituted styrene has

been difficult to form, since the condensation due to dehydro-

chlorination has been extremely easy to take place among

them.

Department of Synthetic Chemistry,

Kyoto University : Yoshida, Kyoto,

Faculty of Engineering,

Japan

Reactions

Ethylene

Kogyo Kagaku Zasshi 74,

of Dihydroxy-p-benzoquinones

Glycol

by Teruzo

Shinsaku

ASAHARA,

SHIRAISHI

231

with

Manabu SENO,

and Takuma TESHIROGI

(1971)

Reactions of 2,5-dihydroxy-p-benzoquinone, 2,5-dichloro-

3,6-dihydroxy-p-benzoquinone and 2,5-dibromo-3,6-dihy-

droxy-p-benzoquinone with ethylene glycol were investigated

in the presence of H2SO4, HC1, or HBr as catalyst. Some

tetrahydroxybenzene ethylene ethers were derived as reac-

tion products, structures of which were analyzed by means

of IR, NMR and mass spectra, and a general reaction scheme

was proposed.

Institute of Industrial Science, The Roppongi, Minato-ku, Tokyo, Japan

University of Tokyo:

Preparation of

Acids*

by Shungo

Kogyo

Fluorine

Kagaku Zasshi 74,

Containing

SUGAWARA and

(1971)

Biphenyldicarboxylic

Nobuo ISHIKAWA**

In order to find suitable monomers for the production of thermally stable polyamides or polyesters, several poly-fluorinated biphenyldicarboxylic acids have been prepared.

sym-Polyfluorobiphenyls were prepared by aryl-aryl oxi-dative coupling of di- or tri-fluorolithiobenzenes using cupric chloride, or by Ullmann coupling reaction of difluoroiodo-benzenes in dimethylacetamide. Polyfluorobiphenyls or poly-fluorobromobiphenyls were lithiated and the resulting dilithio compounds were carboxylated giving the following poly-fluorophenyldicarboxylic acids : 3,3',5,5'-tetrafluorobipheny1- 4,4'-dicarboxylic acid, 2,2',4,4'-tetrafluoro-3,3'-dicarboxylic acid, 2,2',4,4',6,6'-hexafluorobiphenyl-3,3'-dicarboxylic acid

[9]. 2,2',6,6'-tetrafluorobiphenyl-3,3'-dicarboxylic acid, 3,3'6,6'-

tetrafluorobipheny1-2,2'-dicarboxylic acid and [9] were also prepared in low yields by lithiation and oxidative coupling of the corresponding polyfluorobenzoic acid.

Diamides and dimethylesters of these polyfluorobiphenyl-dicarboxylic acids were also prepared.

* Synthesis of Fluorinated Aromatic Monomers . VI. ** Department of Synthetic Chemistry , Faculty of Engineering,

Tokyo Institute of Technology : Ookayama, Meguro-ku, Tokyo,

Japan

Kogyo Kagaku Zasshi

Kogyo Kagaku Zasshi 74, 240 (1971)

Effect of Substituents on Base-Catalyzed Azo

Coupling Reaction*

by Yaji HASHIDA, Shizen SEKIGUCHI

and Kohji MATSUI**

The influence of ortho-substituents of diazo components on the base-catalyzed azo coupling reaction has been inves-tigated kinetically. Small base catalytic effect was observed in the reactions of ortho [C113, C2H5, CH (CH3)2, OCH3, NO2

(p-OCH3), Cl (p-OCH3), C6H5, 2,3-(CH2)41 substituted benzene-diazonium salts with 2-naphthol-3,6-disulfonic acid (R-acid). However, in the reaction of unsubstituted and ortho (503H) substituted derivatives with R-acid the base catalysis was not observed.

In the case of the reaction with 2-naphthol-6,8-disulfonic acid, the reaction was strongly accelerated by the bases and the base catalytic effect varied with the nature of the substituent in the benzenediazonium salts.

These results are discussed in term of the reactivity of the diazo component.

Studies on Azo Colors. VII. ** Faculty of Technology, Gunma University: Kiryu, Gunma, Japan

Kogyo Kagaku Zasshi 74, 243,---'247 (1971)

Antioxidant Dyes for Polypropylene Fiber

by Kiroku KOMATSU*, Shigeo KISHIMOTO**

and Nobuhiko KUROKI*

Polypropylene fibers are being used in a variety of ap-

plications, but one of the deficiencies of the fibers is its

succeptability to heat- and light-induced oxidation. The

ordinary antioxidants in the fiber are lost easily during

laundering, drying and dyeing.

The antioxidant dyes were prepared by combining anti-

oxidant residue and chromophore with triazine ring. Using

the new type of dyestuff, coloring and improvement of heat-

stability of the fiber were achieved simultaneously by a

process of dyeing.

Both oven aging time of the dyed fibers and the measuring

of induction period of dyed films at 140°C by oxygen uptake

method showed the excellent antioxidant properties of

prepared dyes.

* Department of Applied Chemistry , Faculty of Engineering, University of Osaka Prefecture: Mozu, Sakai, Osaka, Japan

** Dainippon Ink Chemical Ind . Co., Ltd. : Ichihara, Chiba, Japan

Kogyo Kagaku Zasshi 74, 247,---,252 (1971)

Treatment of Japanese Coal with Sulfuric Acid for the Preparation of Cation-Exchanger*

by Kohei URANO** and Raisaku KIYOURA***

The present study was undertaken to make clear the effect of the treatment of 19 coals and 2 semi-cokes with H2SO4 for the preparation of cation-exchanger.

The optimum temperature for the treatment was about 80°C, at which the cation exchange capacity (C.E.C.) increased

fully by the treatment for 2'—.3 hrs. The treatment of the coals except for an anthracite and 2 semi-cokes under sui-table condition gave the products with similar total C.E.C.,

pore-size distribution, and density, though carbon contents of the raw coals were varied from 66 to 89w. The total

Vol. 74, No. 2 (1971) A15

C.E.C. was 1.7+0.3 meq/g, in which the C.E.C. for sulfonic acid group and that for carboxylic acid group was in the range from 0.5 to 1.2 meq/g, respectively. The anthracite and the semi-coke were rather less ractive, and gave the

products with rather small C.E.C.. The reaction of the treatment with H2SO4 was not only sulfonation but also oxidation, and released SO2, CO2, and CO. Coals of higher carbon contents were oxidized more easily.

Adsorbents and Ion-Exchange Materials from Coal. IV. ** Resources Research Institute , AIST, MITI : Ukima, Kita-ku,

Tokyo, Japan *** Tokyo Institute of Technology : Ookayama, Meguro-ku, Tokyo,

Japan

Kogyo Kagaku Zasshi 74, 253----,256 (1971)

Effects of Lipid on Collagen Films*

by Isao KARUBE, Takashi KANEKO,

Shuichi SUZUKI and Jun MIZUGUCHI**

The electrochemical forming of films and strings from fibrous protein has been developed by the authors.

The raw material of these products, tendon, skin, etc., contains a considerable amount of lipid. In this paper, effects of lipid on mechanical properties of collagen films are described.

Lipid in tendon of sperm whale was extracted by treat-ment with organic solvent (chloroform-methanol 1 : 1). Mechanical strength of the electrochemical forming films increased proportionally with decreasing lipid content. On the other hand, it decreased with addition of lipid.

These results are cosidered to indicate that lipid in film may prevent fibrils from entangling.

* Studies on Electrochemical Forming of Fibrous Protein Films . IV.

5* Research Laboratory of Resources Utilization Tokyo Institute of Technology : Ookayama, Meguro-ku, Tokyo, Japan

Kogyo Kagaku Zasshi 74, 256---,259 (1971)

Characteristics of Cellulase Hydrolysis of Cellulose

Materials

by Yoshitaka OGIWARA, Ken-ichiro ARM

and Masataka YAMAMOTO

In order to analyze enzymatic hydrolysis of cellulose ma-

terials kinetically, the methods for estimation of kinetic

parameters were investigated. In most reports, the para-meters have been estimated from the increase in reducing

power of reaction mixture. However, we have found that the soluble hydrolysates produced in this reaction using a

commercial cellulase mainly consist of glucose and cellobiose,

and the proportions of both reducing products as well as

their amounts remarkably change with the progress of the

reaction. Therefore, the methods for estimation of kinetic

parameters from the weight loss of hydrolyzed cellulose fiber were examined instead of that from the increase in reducing

power of reaction mixture. As a result, the kinetic para-meters could be accurately estimated from Hofstee's plots of

the reaction rates represented by the weight loss of cellulose

fiber after 24-hours hydrolysis. It was also found that these

parameters varied with the fine structure of cellulose fiber used. It was conccluded that some information on the fine

Al6 Kogyo Kagaku Zasshi

structure of cellulose fibers might be obtained by comparing

such parameters of various cellulose fibers.

Department of Chemistry, Faculty of Engineering, Gunma

University: Kiryu, Gunma, Japan

Kogyo Kagaku Zasshi 74, 259,--i265 (1971)

Photoconduction of Polyamides*

by Ryo HIROHASHI, Yasushi HISHIKI and Masaaki DOHI**

In order to elucidate the effect of molecular structure on the photoconductivity, polyamides were prepared by the poly-condensation of terephthaloyl chloride (TPC) , isophthaloyl chloride (IPC), Adipoyl chloride (ADC) with p-phenylenedi-amine (PDA) , benzidine (BD) , 1,5-naphthylenediamine, 4, 4'- diaminodiphenylsulfone, 3, 3'-dichloro-4, 4'-diaminodiphenyl-methane (CPM) , hexamethylenediamine (HMD) and 3, 9- bis(3-aminopropyl) -2, 4, 8, 10-tetroxaspiro(5, 5)-undecane

(SPIRO). In the temperature dependence curve of specific resistance

of compressed samples, a kink was found for many poly-amides. The values of the activation energy (EA) for the dark conductivity and the specific resistance were ; poly-amides containing terephthaloyl group p = 1012-1015 ohm cm,

EA=0.20-1.11 eV, polyamides containing isophthaloyl group p = 106-1014 ohm. cm, EA = 0.35-4.54 eV, polyamides con-

taining adipoyl group p=108-1015 ohm•cm, EA=0.08-0.87 eV. Photo-current was found to be smaller in the air (APC-

PDA, id=1.06 x10-" Amp) than in vacuum (ip=4.36x 10-1° Amp, 10-6 Torr.).

The ratio of photo-current to dark-current was found to be in the following order; APC-PDA 9490>TPC-HMD 7750 >APC-BD 7160 > TPC-PDA 2480 > IPC-SPRIO 1180 > TPC-CPM 997.

Electrical Conductivities of Organic Polymers. XII. ** Faculty of Engineering, Chiba University: Yayoi-cho, Chiba,

Japan


Role of Poly(vinyl alcohol) on Adhesion of Diallyl-

phthalte Resin and Dichromate-treated Copper Foil*

by Shigeo NARA and Kentaro MATSUYAMA**

It was found that the dichromate-treated copper foil had an adhesive strength with diallylphthalate resin. It was concluded that adhesive strength was due to the chemical affinity of allyl groups and Cr(11) ions formed on the copper surfaces by the treatment of the adherend.

It was observed that the treatment of the adherend with poly (vinyl alcohol) strengthen the adhesive bonding with diallylphthalate resin, and this effect was further streng-thened by addition of pottasium dichromate into poly(vinyl

alcohol). Cr(u) is reduced to Cr(ill) by heating and Cr (la) forms

the crosslinking with hydroxy groups in poly(vinyl alcohol) by ligand banding.

Based on the above considerations, the mechanism of for-mation of these adhesive bonds have been discussed.

Studies on Adhesion of Allylic Resin. II. ** Ibraki Annex, Electrical Communication Laboratory:

Tokai-mura, Ibaraki-ken, Japan

Vol. 74, No. 2 (1971)

Kogyo Kagaku Zasshi 74, 269^-,272 (1971)

Contractile Systems of Polyvinyl Alcohol Films in Metal Amine Complexes Aqueous Solution

by Nobumasa HOJO, Hirofusa SHIRAI, Yoshio KAMEYAMA, Keno NAGASAKI

and Shinzo ICHIKAWA

Water insoluble films of polyvinyl alcohol (PVA) were suspended in metal amine aqueous media and the relative lengths measured as a function of pH, ion concentration, ion strength and species of anions and metal ions. Shrin- kage of the PVA film in metal amine due to bivalent com-

plexes were observed only in the case of copper( Tr) ion. Percent of shrincage of PVA film was nearly proportional to adsorbed ammounts of copper(ff ) ion. Study of infrared spectra is presumed that the copper( ion is bounded to hydroxyl group of the side chains in PVA films, and so film shrunk. From the X-ray diffraction studies, the crystalli-zation of PVA film were found to increase by shrinking in

copper( Ii) amine complex aqueous solution.

Faculty of Textile Science and Technology, Shinshu University: Ueda, Nagano-ken, Japan


Contactile Systems of Phosphorylated Polyvinyl Alcohol Films in Metal Ion Aqueous Solution

by Nobumasa HMO, Hirofusa SHIRAI and Teruo MORI

Water insoluble films of phosphorylated polyvinyl alcohol

( I ), cross linked with formaldehyde were suspended in metal ion aqueous media, and their relative lengths measured as a function of pH, ion concentration, ion strength, and species of anions and metal ions. The films of ( I ) in the swollen state shrunk in acid and various electrolyte aqueous media and the relative lengths of shrinking were increased in presence of copper(in ion. These phenomena cause formation of coordination bond between the phosphate groups in ( I ) and copper( II ). These results were interesting com-

pared with those obtained for polyvinyl alcohol films in metal ammine complexes aqueous solution.

Faculty of Textile Science and Technology, Shinshu University: Ueda, Nagano-ken, Japan

Kogyo Kagaku Zasshi 74, 277,--•281 (1971)

GPC Measurements in Various Solvents*

by Masamichi IWAMA and Terutake HOMMA**

The effect of the power of solvents for GPC chromatograms

and the universal calibration curve were investigated by

using various solvents, i. e. cyclohexane, MEK, THF, and

toluene, in columns packed with porous glass beads as well

as with polystyrene gel. The glass beads were selected so

as to keep the pore size unchanged in these solvents.

The adsorptive property of polystyrene in cyclohexane on

the glass beads was observed by the fact that the recovery

of polystyrene from these columns was almost zero. An

investigation was done by silanization to get glass beads

with complete recovery.

GPC chromatograms measured in various solvents by using

glass beads thus treated showed complete recovery of poly-styrene in cyclohexane, and the universal calibration curve

Kogyo Kagaku Zasshi

did not hold in these solvents. Among the molecular

weight distribution curves obtained from these chromato-

grams, those measured in cyclohexane was slightly affected by adsorption.

GPC measurements of polystyrene on the polystyrene gel

columns in cyclohexane showed no complete recovery, and

the universal calibration curve did not hold in these solvents

also.

* Polymer Characterization by GPC . IV. ** Research Laboratory, Japan Synthetic Rubber Co., Ltd. :

Mochiizaka, Ikuta, Kawasaki, Japan

Kogyo Kagaku Zasshi 74, 281,—,287 (1971)

Amorphous Orientation Evaluation of Polypropyrene

from Dye Dichroism

by Masao SUMIDA, Keizo MIYASAKA

and Kinzo ISHIKAWA

Change in the amorphous orientation with drawing of

isotactic PP was investigated by dichroisms of fluorescent

dye, iodine and IR amorphous band.

The amorphous orientation factors by these methods were

compared with those deduced from X-ray diffraction and

birefringence.

PP film was drawn at 60°C water. The amorphous orien-

tation factors determined from the dichroisms of dye, iodine

and IR amorphous band, increased monotonously with draw

ratio, whereas the amorphous orientation factor determined

from birefringence and X-ray diffraction took negative values

in a range of low draw ratios.

These results were discussed in relation to the intrinsic

values of birefringence of the crystalline and amorphous

regions.

Laboratory of Textile Physics, Tokyo Institute of Technology : Ookayama, Meguro-ku, Tokyo, Japan

Kogyo Kagaku Zasshi 74, 287/--d295 (1971)

Effects of Block Sequence Length on the Linear

Viscoelastic Properties of Styrene-Butadiene Copolymers

by Teizo KOTANI and Yutaka KUWABARA

A series of styrene-butadiene multi-block and random co-

polymers were synthesized by means of the anionic poly-merization technique with n-butyl lithium as an initiator.

The sequence lengths of styrene and butadiene blocks were

regulated to be unchanged for each sample. A series of

samples of different block sequence lengths were prepared

while their styrene contents and the average molecular

weights were kept constant. Various techniques such as

gel permeation chromatograph, osmometry, intrinsic viscosity measurements, NMR, infrared absorption spectroscopy,

electron microscope and others were employed to characterize

the samples. A pochettino type relaxometer and a viscoela-

stic spectrometer were used to obtain the relaxation moduli

of the samples in both transition and rubbery regions.

From the analysis of the mechanical data with respect to

the calculated lengths of styrene block sequence, iis, the

following conclusions were obtained. With increasing ns,

the fractional free volume of the system first decreases to

hit the minimum at around 25<ñ<40 and then increases

rather rapidly but finally levels off. At an iso-free volume

state, the shift factor, log al, was the same for each sample

of those with fis<40, and followed the WLF equation, but

Vol. 74, No. 2 (1971) A17

deviated downwards at and above 60°C from the WLF for

those with fis>40. The shapes of the isochronal relaxative

moduli of those with n<40 resemble the modulus of a

random copolymer whereas for those with fis>40 were

similar to that of a polyblend, and an intermedium type

appeared at fis=40.

Research Laboratories of Japan Synthetic Rubber Co. : Mochiizaka, Ikuta, Kawasaki, Japan


Effects of Some Metal Salts on the Polymerization of

Methyl Methacrylate Initiated by the System of

Cellulose-Water-Carbon Tetrachloride*

by Yoshio IKI, Masayoshi KINOSHITA

and Minoru IMOTO**

Several kinds of celluloses were analyzed by activation

analysis to include a trace amount of metals such as zink,

copper, manganese etc. The effect of the addition of several

metal salts on the polymerization rate of methyl methacrylate

initiated by the system of cellulose, water and carbon tetra-

chloride was studied and it was concluded that cupric salts

accelerate excellently the polymerization in this system and

the acceleration of polymerization rate is caused by the

adsorption of cupric ion on the cellulose. The effects of the

amounts of water, carbon tetrachloride and methyl metha-

crylate on the polymerization rate were found to be ana-

logous to those in the case of the original celluloses. The

important role of copper in natural celluloses in this poly-

merization system was deduced from these results.

* Vinyl Polymerization . 256. ** Department of Applied Chemistry , Faculty of Engineering,

Osaka City University : Sugimoto-cho, Sumiyoshi-ku, Osaka, Japan

Kogyo Kagaku Zasshi 74, 298,---'301 (1971)

Esterification of Styrene-Maleic Anhydride Copolymer by Mixed Alcohols

by Jar° AOYAGI, TOru TAGAWA and lsao SHINOHARA

A copolymer of styrene and maleic anhydride (MW =1,800) was esterified with excess amount of alcohol mixture and the relation between the esterification rates of the individual alcohol and the contents of the esters in the esterified co-polymer was discussed. At first, the individual rate con.- stants of esterification of each four alcohols (n-butanol, butanol, i-amylalcohol, benzylalcohol) were decided in non-catalyst system. Then, mixed esterification with mixture of n-butanol and i-amylalcohol was carried out and, from the analysis of the ester contents of the product, the fol-lowing relation was obtained : [P1]/[P2]=ki[Bi]/k2[B2]• From this result, it can be concluded that, in the esterification with alcohols involving n species, the content of the individual ester is expressed by the following eqation.

EPA/En[Pi]E ki[Bdo, (i, j=1,••-, n)

i

where [P] ; ester contents in the copolymer

[B]0; initial concentration of alcohol k ; rate constant for the esterification

Dspartment of Polymer Chemistry, Waseda University: Shinjuku-ku, Tokyo, Japan

Alb Kogyo Kagaku Zasshi

Kogyo Kagaku Zasshi 74, 301,...,305 (1971)

Synthesis of N-VinyI-5,5-dimethylhydantoin Derivatives*

by Minoru SASHIO, Makoto TANAKA and Niro MURATA**

For syntheses of 3-vinyl-hydantoin derivatives, the pyro-lysis of 3-a- and 3-8-acetoxyethyl derivatives of 5, 5-dime-thylhydantoin (DMH) and 1-alkyl-5, 5-dimethylhydantoin (1- alkyl-DMH) were studied.

3-a-Acetoxyethyl derivatives were synthesized by the reaction of hydantoins with vinyl acetate in the presence of

potassium hydroxide at 100-170°C. From DMH, 1-acetyl-3-a-acetoxyethyl-DMH I ) formed.

in high yield. 1-Alkyl-DMH gave 3-a-acetoxyethyl derivatives (R=-CH8(I[ ), C2115(B1)) in high yield at 100,-,150°C, but at 170°C the yields were reduced because of the formation of 3-vinyl derivatives as main product.

3-9-Acetoxyethyl derivatives were prepared by the reac-tion of hydantoins with ethylene chlorohydrin followed by acetylation. Pyrolysis was carried out by passing a 30$ acetone solu-

tion of acetoxyethyl derivatives at a velocity of 1 mi/min through a stainless tube at the prescribed temperature.

(n) and (m) gave 3-vinyl derivatives in 85-950 yields at 450° and 500°C. On the other hand, products from ( I) were 1-acetyl-3-vinyl-DMH and 3-vinyl-DMH.

3-j3-Acetoxyethyl derivatives gave 3-vinyl derivatives, but the yields (20—'700) decreased with the rise of temperature over 520-590°C.

1-Vinyl-3-ethyl-DMH was obtained by the prolonged reac-tion of 3-ethyl-DMH with vinyl acetate in the presence of mercuric acetate and sulfuric acid at ordinary temperature.

* Studies on Hydantion Derivatives. V. ** Department of Applied Chemistry, College of Engineering.

University of Osaka Prefecture: Sakai, Osaka, Japan

Kogyo Kagaku Zasshi 74, 306—d312 (1971)

Scission Reaction with Stabilization of Polyoxymethylene by BF3OEt2 in Acetic Anhydride*

by Takami ISHII and Naohisa TAKIGAWA**

The methods of stabilization and control of the molecular weight of polyoxymethylene (POM) in acetic anhydride (Ac20) solution by BF30Et2 as catalyst have been studied, and the following results were found : 1) The chain-scission of the POM took place to produce polyoxymethylene diacetate with the regulated molecular weight. 2) Resultant polymers were obtained in the quantitative yield (1000), and its number average molecular weight decreased with the reaction time. 3) The rates of scission reaction were found to be proportional to the first order of the concentration of

BF30Et2 or BF30Ac2. 4) The thermal stability of the cleav-ed polymer was increased to the practical property (k222=

0.3). The k222 value decreased with increasing the molecular weight of the source POM. The cleaved chainends of the resultant polymer were quantitatively introduced to acetyl groups (1000) and the OH groups of the source POM re-mained without acetylation at ordinary temperature. The relation between the acetylated-polymer contents (W) and the number (N) of the scission was calculated by the equa-

Vol. 74, No. 2 (1971)

tion, W---= (N-1)1 (N+ 1). 6) BF30Ac2 complex was obtained from BF30Ac2 in Ac20 and also ethyl acetate was quantita-tively obtained from Ac20 and diethylether by BF30Et2 at ordinary temperature. The results suggest that the scission reaction of POM proceeds by the following inserted acetyla-tion mechanism : In the first place, BF30Ac2 complex is

produced by ligand-exchange reaction of BF30Et2 in excess amounts of Ac20, then the -C-O- bond of POM is coordinated with the BF30Ac2 complex and the cleavage of its bond

proceeds with acetylation.

* Catalytic Scission Reaction of Polyoxymethylene. I. ** Tokyo Polymer Research Laboratory, Ube Industries Ltd,

Goi, Ichihara, Chiba, Japan

NOTES


Some Considerations on the Behavior of Particles in a

Moving Bed

by Hiroshi YANAI, Tadanobu HAYASHI,

Tadashi TAKEDA and Tamio OKUBO

In an attempt to determine the behavior of particles

within a moving bed, the vertical section profiles of tracer

distribution have been studied by the photographic observa-

tion and its analysis, using several tracer particles of dif-

ferent properties.

Based on the analysis of the distribution curves it is found

that the bed consists of two groups, namely, core particles

and particles near a tube wall.

The critical radius r, changes when the travelling distance

is shorter than four times of a tube diameter, independently

of the tube diameter, the property of particles, and travel-

ing rate. It may be concluded that the lagged distance of

particles at a tube wall is directly proportional to the travel-ing distance and it is influenced by both the property of

particles and traveling rate.

Department of Chemical Engineering, Muroran Institute of Technology : Mizumoto-cho, Muroran, Hokkaido, Japan

Kogyo Kagaku Zasshi 74, 314,--,3[6 (1971)

Synthesis of Linear Dibenz[b,i] acridan-13-one

by Hisao NISHI, Susumu ICHIKAWA and Yoshio NAGAI

Linear dibenz[b, i]acridan-13-one (vi) was synthesized by the following method in three steps.

i ) Dibenz[b, acridan-5, 13, 14-trione (Y) was prepared in 870 yield by cyclization of 2- (3-carboxy-2-naphtylamino)- 1, 4-naphthoquinone (il) in polyphosphoric acid at 130°C for 1 hour.

N was reduced with polyphosphoric acid and zinc powder at 150°C for 2 hours to dibenz[b, i]-5, 14-dihydro-acridan-13-one (v) in 980 yield.

iii) a) V was oxidized with sodium-nitrobenzene-m-sul-fonate, and the product was purified by subliming in glass tube at 10-5 mmHg, 300°C. vl was obtained as reddish violet prizm.

Kogyo Kagaku Zasshi Vol. 74, No. 2 (1971) A19

b) v was also oxidized to 11 with copper powder under reduced pressure.

m. p. 407°C, is sublimable reddish violet needle with metallic luster.

It is soluble in organic solvent with yellowish red color and in 112SO4 with greenish blue color.

Faculty of Science and Engineering, Saitama University: Shimo-Okubo, Urawa, Japan

Kogyo Kagaku Zasshi 74, 316---'318 (1971)

Reaction of 1-Methyl-imidazole-4,5-dicarboxylic Acid

with Phosphorus Pentachloride

by Keiryo MITSUHASHI, Kazuyuki TAKAHASHI, Tadataka ZAIMA and Teruzo ASAHARA

The reaction of 1-methyl-imidazole-4, 5-dicarboxylic acid with phosphorus pentachloride gave 1-methyl-4-trichloro-methyl-imidazole-5-carboxychloride ( I ). The structure of the product I was verified from those of several derivatives obtained by the reactions of I with water, methanol, am-monia, aniline, and phenols respectively. Some of these derivatives have not been reported yet.

Department of Chemistry, Seikei University : Kitamachi, Kichijoji, Musashino, Tokyo, Japan


Behavior of Methylmercury Compounds in Hydration of

Acetylene

by Koji TERAMOTO, Hiroshi ABE,

Yoshihiro MURAYAMA, Yoshitaka NOGUCHI,

Hiroshi MARUYAMA and Hideo ICHINOKAWA

A study was conducted on the behavior of methylmercury compounds during the hydration of acetylene, using a mer-cury catalyst in a bubble tower type continuous reaction apparatus. It was observed that the concentration of methylmercury

sulfate in the catalyst solution reached an equilibrium con-centration of 2.6 peg under steady state conditions. This indicates that under industrial operation conditions the con-centration of methylmercury compounds is maintained only at a fixed low value and does not increase with the amounts of acetaldehyde.

It was observed that methylmercury compounds were decomposed by peracetic acid which is considered to be formed during the formation of acetic acid in the reactor.

Showa Denko Co., Ltd. : Shiba Miyamoto-cho, Minato-ku, Tokyo, Japan

kogyo kagaku zasshi - j-stage

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