Kogyo Kagaku Zasshi - jstage.jst.go.jp

Kogyo Kagaku Zasshi

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

Vol. 68, No. 9, pp. 1629•`1810 (1965)

Abstracts

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

ORIGINALS

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Kogyo Kagaku Zasshi 68, 1629 -1634 119651

Thermal Decomposition of Cobaltous Acetate Tetra-

Hydrate

by Teruichiro KUBO* and Kazuo MANAGE**

The process of thermal decomposition of cobaltous acetate

tetra-hydrate is studied by DTA, TGA, and X-ray diffrac-

tion methods.

The following results are obtained:

The DTA pattern of cobaltous acetate tetra-hydrate depends

remarkably on the thickness of packing layer of specimen

prepared. When the thickness of packing layer of specimen is 1 mm., one endothermic and one exothermic peaks appear

in the DTA pattern, but with 20 mm, specimen, they separate

distinctly into five endothermic and one exothermic peaks in

the DTA pattern.

The dehydration of four molecular crystal water begins

at about 50°C, and two unknown hydrates are produced in

the process of the dehydration.

Cobaltous acetate anhydride which is unstable at the

temperature above 90°C, decomposes continuously after the

completion of the dehydration, and two intermediate com-

pounds are produced during the process of thermal decom-

position. These intermediate compounds are found to be new substances, perfectly different from every known

cobaltous compound.

Cobaltous oxide is first produced by the thermal decom-

position of the second intermediate compound, and then it is oxidized to tricobalt tetraoxide in air.

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

** Department of Engineering , Tokai University : Yoyogitomigaya, Shibuya-ku, Tokyo, Japan

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Kogyo Kagaku Zasshi 68, 1634^-1636 119651

New Crystalline Phase of SiO2 ' Fe2Og Gel Prepared from Iris (hydroxydiphenylsiloxy) iron

by Sugio OTANI, Akira KOJIMA and Yasuaki NAKAIDO

Tris (hydroxydiphenylsiloxy) iron, Fe(OSiph20H)s (1), and the amorphous compound (2) having Fe-O-Si bond were prepared by the reaction between FeClg, ph2Si(OH)2 and Nile. The chemical compositions of the Fe20$•Si02 gels

obtained from the above two samples by heating in air at and below 500°C were as follows respectively; (I) Site 67.5

s,', Fe2Os 32.5 o, (2) Si02 30.6 /, Fe2Os 69.4 %. The crystallographic transformation of gels in air in the temper-ature range of 7001500°C was studied by means of X-ray diffraction analysis. From the obtained results, it is con-firmed that the new crystalline phase exists in the gels

prepared from (1) by heating between 1100 and 1250°C. We name it N-ferrosilicate phase. The spacings (A) of this phase are as follows: 3.22w 2.97m 2,72s 2,55w 2.46m 2.24w 1.73w 1.52w 1.47w

Attempts to determine the crystal system of the new

phase were unsuccessful.

Faculty of Engineering, Gumma University Tt'njin-cho, Kiryu-shi, Japan /1111111111/i11i r1 /Iti11rf 1111 {IIIilIf11f 11/1/1111111111111/1l/1111 II t111111111Ii YY YYYYYY YY rr IIr Ir1/1Yi1Irf

Kogyo Kagaku Zasshi 68, 1636^-'164` 119651

The Influences of Pretreatment and Oxygen

on Corrosion of Aluminium

by Masayoshi KATOH

In order to examine the reproducibility and the mechanism

concerning corrosion of aluminium in 1N NaOH and in

1N HCl solutions, the influences titled above were studied.

The rate of corrosion, concentration of of dissolved oxygen

and potential variation with time when the specimens are

anodically polarized were measured, where the latter two

measurements were performed utilizing polarograph and

synchroscope, respectively. The measurement by synchros-

cope was found to be a powerful method for detection

of oxide film on the specimen.

Formation of the oxide film on aluminium was comfirmed

when the specimen was dipped in water for only a minute

or when it was exposed in air.

The presence of the oxide film on aluminium prior to

corrosion showed a considerable influence on the initial rate

of the corrosion. In NaOH solution, the oxide film formed

by pretreatment accelerated the local cathodic reaction until

the film was dissolved out, and hence the initial rate of cor-

rosion was accelerated, while in HC1 solution in which the

local anodic reaction was highly restricted the film previ-

ously formed depressed the reaction further.

The dissolved oxygen had no effect on the rate of corrosion

in NaOH, but it accelerated the initial rate of corrosion in

HCI.

Department of Applied Chemistry, Faculty of Science, Tokyo College of Science : Shinjuku-ku, Tokyo, Japan

IrIr1i11/1Jif Y1l rll YYY it YY Yr/1 YYYY YY YY/1 Rr1 YYY YYr II/rIt111r1r11/Iii lrti1/1r11 trt1rrlrr/l/iri/rlrrrrlrrr ilrl

A 100 Kogyo Kagaku Zasshi Vol. 68 No. 9 (1965)

Kogyo Kagaku Zasshi 68, 1642^y1645 (1965}

The Mineral Composition and Thermal Behavior of the

Aluminium Phosphate Ore of Brazil

by Tsuyoshi ARIMORI, Naojiro YOSHIDA

and Saburo KATAOKA

In order to investigate the mineral compositions of the aluminium phosphate ore of Brazil, the microscopic obser-vation and the X-ray analysis of the sample were per-formed.

These experimental results were as follows, The main mineral compositions of the lower and the middle layers of Trauira Island are wardite and crandallite, and those of the upper layer of this island are variscite, goethite and hematite. The main mineral compositions of the Pirocaua Hill are augerite, hematite and goethite. Next, the thermal behaviour of the samples of the lower and the middle layers of Trauira Island were investigated. Namely, the differential thermal analyses of these samples and the X-ray analyses of the calcined samples were carried out.

According to these results, it is confirmed that the weak endothermic reactions at 130°C and 400°C are due to the dehydration of the crystalline water, and the strong endo-thermic reaction at 550°C is due to the dehydration owing to the dissociation of the crystals of wardite and crand-allite, and also the samples become to the amorphous state at that temperatue. The strong exothermic reaction at 750°C is due to the formation of x-cristobalite AIP0} and 3Ca0 5A1203.

Institute of Ceramics, Faculty of Industrial Art, Kyoto Technical University : Matsugasaki, Sakyo-ku, Kyoto, Japan

Kogyo Kagaku Zasshi 68, 1646^,1651 (1965)

Concentration of Electrolyte Solutions by Electrodialysis through Ion Exchange Membranes.

I. Mechanism of Concentrating Salts

by Masayasu TASAKA and Ikumi KAGAWA

Various heterogeneous ion exchange membranes were

prepared with polyvinylchloride as a binder. A seven com-partment dialytic apparatus constructed with the mem-branes was used for concentrating electrolyte solutoins. No solution was poured into the concentrating compartment from outside and the quantity transported into the concent-rating compartment through membranes was allowed to overflow. After a steady state was reached, the volume and concentration of the overflowing solution were measured. It was assumed that an electrolyte transport is caused by the two independent processes, by electrical transport and by free diffusion, and also that a water transport is caused by both electroosmosis and free osmosis. From the analysis of the experimental data it was shown that the free electrolyte diffusion is practically negligible compared with the total electrolyte transport, whereas the free osmosis of water is a considerable part of the total water transport.

Department of Applied Chemistry, Faculty of Engineering, Nagoya University : Nagoya, Japan

Kogyo Kagaku Zasshi 68, 1 651 -164 (196':,

Concentration of Electrolyte Solutions by Electrodialysis

through Ion Exchange Membranes.

II. Energy Consumption in Concentrating Salts

by Masayasu TASAKA and Ikumi KAGAWA

The effects of electric resistance, transport number of

membrane and current density etc. on the electric energy

consumption were studied. A sample solution was continu-

ously flowed through the desalting compartment in order to

keep the concentration constant. At the beginning the

concentrating compartment was filled with the sample

solution, and the concentration of the solution was allowed

to increase as the electrodialysis was carried on. The

energy consumption calculated from the voltage, current

and amount of salt concentrated was compared with those

calculated from the membrane resistance etc. The agree-

ment was satisfactory.

The effects of the concentration of the sample solution

and the current density on the energy consumption were

discussed using the results of our previous work.

Department of Applied Chemistry, Faculty of Engineering, Nagoya University : Nagoya, Japan

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Kogyo Kagaku Zasshi 68, 1655^1661 (1965)

Concentration of Electrolyte Solutions by Electrodialysis

through ion Exchange Membranes,

Ill. Two Step Concentration

by Masayasu TASAKA, Haruhiro HIRAI

and Ikumi KAGAWA

A conventional apparatus for concentrating salts by electro-

dialysis, which consisted of a series of alternate concent-

rating and desalting compartments, was constructed by using

cation and anion exchange membranes alternatively. As

the salt concentration in the concentrating compartment

increases, the osmotic pressure difference between concent-

rating and desalting compartments becomes high. There-

fore, the water transport due to the free osmosis increases,

and, consequently, the concentration in the concentrating

compartment can not become high. In order to decrease

such osmotic flow, the concentrating compartment was

divided into three compartments, and new cation and anion

exchange membranes which have lower transport numbers

were inserted. By such two step concentration, free osmosis

was considerably decreased, and the average concentration

of all solutions in three compartments became higher than

the concentration reached by the original method. Particul•

any, the concentration of the middle concentrating com-

partment was found to reach the supersaturated state.

I)epnrthnent Of Applied C1unri st ry, I acut t y n f E,,g i neeri rr~ . Nagoya University : Nagooa, Japan

Kogyo Kagaku Zasshi 68, 1661-'-1664 (1965)

The Ionization Mechanism in Radioactive Ionization

Detector

by Shin TSUGE and Tsugio TAKEUCHI

In the field of the radioactive ionization detector of con'

ventional type, studies on the ionization mechanism have

little been made except in the case of organic molecules

Kogyo Kagaku Zasshi Vol. 68 No. 9 (1965) A 101

with ionization potential below 11.6 eV, which is the

potential of metastable argon atoms. In the previous paper, the analysis of inorganic gases

using radioactive ionization detector with a 100 i. C RaD

alpha-ray source, was reported. As a part of this work,

some considerations were given in this paper about ioni-

zation mechanism of molecules with ionization potential

above 11.6 eV.

Ors the basis of following experimental results, namely,

complex dependence of the detector response on the sample

size, the potential applied to the detector and the con-

tamination of carrier gas with organic vapors, the ionization

mechanism was explained in terms of such phenomena as "Penning Effect"

, direct ionization by energitic electrons

and alpha-ray, quenching of metastable argon atoms by

non-ionization collosions with molecules with ionization

potential above 11.6 eV and formation of molecular ion. Oxygen and nitrogen, separated from au by gas chromato-

graphic column packed with Molecular Sieve 5A were used as the sample gas with ionization potential above 11.6 eV.

Argon containing organic vapor, helium and hydrogen were

used as the carrier gas.

Institute of Industrial-Analytical Chemistry, Faculty of Engineering, Nagoya University : Nagoya, Japan

Kogyo Kagaku Zasshi 68, 1665-l669 (1965)

Removal of Thiophene from Benzene by Employing Silica

Gel Column

by Shizunobu HASHIMOTO and Takayuki YAMASHITA

Among various kinds of impurities contained in com-mercial benzene, mercaptans and thiophene are most trouble-some.

The thiophene (0.0037 wt. /) in 400 cc of benzene was completely removed by passing the benzene through an adsorption tower (length, 457 mm. ; inner diameter, 10 mm.; 50'C) packed with 20 g, of silica gel Q28 (100200 mesh), which was previously treated with 9g. of 98 % sulfuric acid. Thiophene was found to be easily self onated by sulfuric acid while being passed through the column and the distri-bution coefficient of thiophene between benzene and sulfuric acid on silica gel was obtained.

Department of Applied Chemistry, Doshisha University : Karasuma-imadegawa, Kamikyo-ku, Kyoto, Japan

Kogyo Kagaku Zasshi 68, 1669^'1674 (1965)

Impurities in Commercial Acetoacetic Acid Methyl Ester

by Tsuneo MOTODA and Yoichi YOSHIE

Five high-boiling point impurities in acetoacetic acid methyl ester (AAM) produced commercially from diketene and methanol were isolated and identified. They were 3-acetoxy-3-butenoic acid methyl ester, diacetoacetic acid methyl ester, two diastereoisomers of 3-acetoxy-2-butenoic acid methyl ester, and trans-enol methyl ether of AAM. Their

gas chromatographic behavior, infrared absorption spectra, and other properties were examined. It is shown that the acetylation of AAM with acetyl chloride and pyridine gives trans- and cis-enol acetates of AAM and that each of the isomers can be determined by gas chromatography .

Central Research Laboratory, The Nippon Synthetic Chemical Co. Ltd, : Kamikema 156, Amagasaki-shi, Japan

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Reaction of Acry/amide with Glyoxal

by Masao YOSHIZAWA and Sachiko TAGUCHI

Novel compounds were produced by the reaction of acryl-amide with glyoxal at 60°C. Using conc. HCl as catalyst, colorless crystals (IA) and a small amount of polymer-like compound (I) were obtained. I, m.p. ). 250°C, had the composition C8H10N208, and was insoluble in most solvents. llA, m.p. 156.158°C (from DMP-benzene), was found to be 1, - 2-diacrylamidoethyleneglycol by micro-analysis, hydro-genation and periodate oxidation. When (C21I5)3N was used as catalyst, a solid (IIB) deposited in the hot reaction mix-

, Lure, and anothdr compound (IV) was obtained from the mother liquor after cooling. IIB, m.p. 153-156°C (from H20), was identical with IIA. IR-spectrum of IV, m.p. 142.5 143.5°C (from H20-C2H5OH), was different from that of JIB, but other analyses gave the same results. IV and JIB were thought to be isomers, but they did not show optical rotation. When JIB was treated with CH80H, C2H5OH, and iso- C3H7OH in the presence of conc. H2SO~, dimethyl-, diethyl-, and diisopropyl-ether of 1, 2-diacrylamidoethylene-

glycol were obtained respectively. However, ethyleneglycol, a-propyleneglycol, and 2, 3-butyleneglycol gave cyclic ethers

(1, 4-dioxane derivatives). IV gave the same products. Treated with diluted acids or bases, IV changed into JIB. From this result, IV was considered to have mesa-structure and JIB to be racemic. 1, 2-Dimethacrylamidoethyleneglycol was produced by the reaction of methacrylamide with glyoxal, but the isomers were not separated by the same procedure. Dimethylether of this compound was synthesized.

Nitto Institute of Chemical Research : 163, Kamikizaki, Urawa--shi, Saitama-ken, Japan

Kogyo Kagaku Zasshi 68, 1680'-1685 (1965)

Solvent Effects in the Decomposition of Benzyl Hydroperoxide

by Yoshinobu TAKEGAMI, Yoshikazu FUJIMURA

and Hiromichi /SHIT

The decomposition of benzyl hydroperoxide in various organic solvents in the presence of cobaltous and cobaltic salt catalysts was studied, and the effective form of catalysts and the distribution of the decomposition products were also examined.

Among the catalysts used, two green-colored substances, i.e., (1) prepared from cobaltous stearate using hydrogen peroxide, and (2) obtained from the air oxidation system of p-xylene by the cobaltous stearate catalyst, showed the same good catalytic activity for the decomposition of the hydro-peroxide. From these experimental facts, the same con-figuration was presumed for these two substances. Cobaltous-acetylacetonate catalyst also showed the catalytic

activity which was comparable to that of the green-colored substances. However, cobaltic-acetylacetonate catalyst had a lower catalytic activity. The decomposition of the hydroperoxide seemed to occur rapidly in the solvents having those active hydrogens which are easily abstracted by radicals,


In such solvents, the distribution of benzyl alcohol, one

of the decomposition products, was found relatively large.

From this it was suggested that hydrogen-abstraction from

solvents has occurred in this reaction.

Faculty of Engineering, Kyoto University : Kyoto, Japan

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Kogyo Kagaku Zasshi 68, 1685^1688 11966)

Reaction of Tricyclohexylboron with Nitrosylchloride -

by Tsuneo OKUSHI,* Osamu MANABE,*

Hachiro HIYAMA* and Zenichi YOSHIDA**

From the reaction products between sulfuric acid solution

of tricyclohexylboron and nitrosylchloride at 80°C in the

atmosphere of nitrogen, the formation of e-caprolactam was

obserbed.

On the other hand, when the reaction was run at 30°C,

N-nitrosodicyclohexylamine was isolated in a good yield.

The reaction of nitrosocyclohexane with tricyclohexylboron

in tetrahydrofuran giving dicyclohexylamine was also

studied, and it was suggested that N-nitrosodicyclohexyl-

amine was produced by the reaction of excess of nitrosyl-

chloride with the dicyclohexylamine formed by the reaction

between tricyclohexylboron and nitrosocyclohexane.

* The Osaka Municipal Technical Research Institute :

38, Kitaogi-machi, Kita-ku, Osaka, Japan ** Department of Synthetic Chemistry , Faculty of Engineering,

Kyoto University : Kyoto, Japan

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Kogyo Kagaku Zasshi 68, 1689^-1692 (1965)

Synthesis of Chloroalkyl Phosphates and Phosphites

by Michio YOSH/NO, Fumihiro MONDEN, Tetsuo IKEDA and Shigeo MUKAI

The reaction condition in synthesizing O=P(OCH2CHC1CH2 Cl)g by reacting epichlorohydrin (I) with phosphorous oxy-chloride is studied with several metal chlorides used as catalyst, the effectiveness of which decreases in the sequence: TiCl4-.'AlC1s>SnCle>BaC12>SiC14 It is found that the reaction proceeds quantitatively at 0.3---0.5 f of TiC14 and 10 % excess of ( I). Based on the above reaction condition, 0=P (OCH2CH2Cl)2 and 0=P (OCH2CHCICH$)2 are synthesized from ethylene oxide ( i[ ). and propylene oxide ( III ), and the esters con-taining two different chloroalkyl groups are also derived from (I) and (II), and (I) and (Ill). Chloroalkyl Phosphites can be synthesized similarly, but

they are found to be inferior to the phosphates in heat stability and antihydrolysis.

Oils & Fats Research Loboratory Nippon Oils & Pals Co., Lid. 56 Ohama-cho, 1-Chome, Amagasaki-shi, Japan

ulrrrrrnru,ufuuunn/,n,»u,/anuu,ufunu,auf.un.r1.111,11/,,,,,/u,nnn,unruu.ur.

Kogyo Kagaku Zasshi 68, 1693'-'--1697 (1965)

Condensation Equilibrium in the Reaction of Terephthalic

Acid with Ethylene Glycol

by Misao SUMOTO and Yukinori HASEGAWA

The esterification reaction was carried out over the range of OH/COON=110 in molar ratio (G) at the temperature

Of 220' to 250°C, in the close4 system, The course p f

the reaction was followed by determining the unreac carboxylic group. The equilibrium constant (KC) waS calculated from the obtained results. An apparent K0 for the esterification reaction of tephthalic acid with ethylene glycol was estimated to be closer unity under the above condition. At the same time, the value of K~ was found to decrease in some extent wits increasing G. '_

It was inferred from consideration on the distribution of molecular species in this reaction system that KC increased with increasing the total concentration of COON and H$0. From this the value of KC was considered to increase by addition of water. The similar experiments made with other kinds of carboxylic acids and alcohols, showed that Kc is much more affected by the type of alcohol than by that of carboxylt~` acid. The heat of the esterification reaction was found t+ be about f 1 kcal. /mol.

Takatsuki Research Institute, Kureha Spinning Co. , Ltd. Nishi-Amakawa, Takatsuki-slti, Osaka, Japan

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Kogyo Kagaku Zosshi 68, 1698-1703 (1965)

The Autoxidation of Alkylidenecyclohexanes

by Hikoichi M1KI, Masumi SAITO, Yoshimitsu MURATA and Yasaburo FUSHIZAKI

The autoxidation of methylene- and isopropylidene-cyclo-hexane was studied to clarify the reaction mechanism of the autoxidation of some of the cycloalkenes. Both methylene- and isopropylidene- cyclohexane were

synthesized from cyclohexanone. The autoxidation was carried out with oxygen in the presence of BPO in a closed vessel. The rate of the oxi-dation was measured under the following conditions: reaction temperature 5075°C, oxygen pressure 50750 mmfg, concentration of alkylidenecyclohexane 0.461.02 mol./l, concentration of BPO 00.06 mol./mol. of alkylidenecy-clohexane, and intensity of ultra-violet light 32^100 0. The hydroperoxides which were detected in the reaction products were decomposed to give the ketones. These were the main reaction products and identified to be 2-methylene-

- and 2-isopropylidene-cyclohexanone. It was concluded, there fore, that the autoxidation of methylene- and isopropylidene-cyclohexane took place at the 2-position of methylene- and isopropylidene-cyclohexane respectively. The initial rate of their oxidation was given by the following expression:

r= ( [ I ] +rTtlki) "2 [RH] [O2] }/(A' [RH] +B' [02] where [ I ] represents the concentration of BPO or the intensity of ultra-violet light and rTt the rate of the thermal initiation reaction. The apparent activation energy of the abstraction of hydrogen was 12 kcal. /mol. in the methylenecycloheXane and 11 kcal./mot, in the isopropylidenecyclohexane.

College of Engineering, University of Osaka Prefecture : Sakai-shi, Osaka, Japan

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Kogyo Kagaku Zasshi 68r 17031705 (1965)

Selective and Competitive Hydrogenation of Aromatic Compounds. I. Competitive Hydrogenation of Non substituted Aromatic Compounds

by Osamu HIBINO, Keizo KINOSHITA, Shiro HASHIMOTO and Keiichi OKADA

The high pressure hydrogenation of non-substituted aro-

matic compounds such as benzene, pyridine, phenol, naph-thalene, quinoline and isoquinoline in the presence of solvent and Raney nickel catalyst were studied. The hydrogenation reactions were carried out near the

temperature at which the absorption of hydrogen occured remarkably, and from the difference of the hydrogenation temperatures, we estimated the relative order of reactivities for hydrogenation as follows; naphthalene > quinoline > benzene phenol > isoquinoline > pyridine. Furthermore, from the results of competitive hydrogenation of the binary mixtures consisting of the compounds above mentioned, we estimated the relative order of reactivities as follows; quinolineisoquinoline>pyridine=naphthalene>

phenol)-benzene.

Tokyo-Laboratory of Research Centei, Yauwala Chenaieal Industry Co. 16I8Ida, Kawasaki-shi, Japan

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Kogyo Kagaku Zasshi 68, 17051707 (1965)

Selective and Competitive Hydrogenation of Aromatic

Compounds, II/ Competitive Hydrogenation of Naphthalene Derivatives

by Osamu HIBINO, Keizo KINOSHITA and Shiro HASHIMOTO

The high pressure hydrogenation of naphthalene and its derivatives such as a- and a-methylnaphthalenes, a- and Q-methoxynaphthalenes, Q-acetoxynaphthalene and j9-acet-aminonaphthalene, and also of binary mixtures consisting of these compounds were studied. The reactions were carried out near the room temperature and in the presence of solvent and Raney nickel catalyst. From the composition of the hydrogenated products we estimated the relative order of reactivities for hydrogenation as follows; $-acetaminonaphthalene>naphthalene> j-acet-oxynaphthalene j Q - methylnaphthalene a - methylnaph-thalene>Q-methoxynaphthalene~; a-methoxynaphthalene.

Tokyo-Laboratory of Research Center, Yawata Chemical Industry Co. 1618 Ida, Kawasaki-shi, Japan

1111111/1H1/J//U///1A///AN11 / / 1 / / 11111{1/11I/IIN1/1/1{1111,11„1111.11/a1111111J 1./r/1i /!rli 1////1//1.

Kogyo Kagaku Zasshi 68, 17071712 (1965)

Fluorescent Brightening Agents of the Naphthalimide Derivatives Containing Basic Group

by Takehito MARUYAMA, Daizo KOBAYASHI,

Nobuhiko KUROKI and Kenzo KONISHI

Fluorescent brightening agents containing basic group, Such as naphthalimide derivatives having N-diethylamino-acetylaminp qr M-piperidylacetylamino group at 4-positon

and 4-acetylaminonaphthal-N-diethylaminoethylimide, p-N-diethylaminoethylsulfamoylaminophenylimide, p-N-piperidyl-acetylaminophenylimide, a- and j-pyridylimide were synthesized. Absorption and fluorescent spectra of these compounds in

solution were measured. The fluorescent maxima of these compounds exist about 460 mp without absorption in the visible region. Applicabilities and brightening effects of these compounds

on several synthetic fibers (Vinylon, Amilan (6-Nylon), cellulose acetate and Cashimilon F (polyacrylonitrile fiber)) were examined. Most of these compounds were found to be adsorbed by Cashimilon F mainly through an electrostatic attraction of these compounds by acidic groups of the fiber. Quaternary salts of 4-diethylaminoacetylaminonaphthal-n-

butylimide and -cyclohexylimide show excellent brightening effect and good fastness to light on Cashimilon F.

Department of Applied Chemistry, College of Engineering, University of Osaka Prefecture : Moxu Umemachi, Sakai-shi, Japan

Kogyo Kagaku Zasshi 68, 1713-'1716 (19651

Reactive Dyes Containing to-Dimethylaminopropiophenone Group

by lroh YAMASE, Nobuhiko KUROKI and Kenzo KONISHI

In order to investigate the reactions between the dyes containing co-dimethylaminopropiophenone group and the fibers containing amino or hydroxyl group, several dyes containing w-dimethylaminopropiophenone group were synthesized as follows. First of all various azo or anthra-

quinone dyes containing acetophenone group were synthesized and then, these dyes were condensed with dimethylamine hydrochloride and paraformaldehyde by Mannich reaction. The reactive dyeings with these dyes were carried out on Amilan (6-Nylon), silk and viscose rayon, and their appli-cabilities, color and fastness were examined. The unfixed dyes on the fibers were removed by soaping, pyridine ex-traction and acetone extraction, w-Dimethylaminopropio-

phenone dyes was found to be fixed well on these fibers and showed an excellent fastness, especially' in the case of 6-Nylon. The color range was yellow, orange, red, violet and blue. The formation of a covalent linkage between the dye and the fiber was confirmed by the method described in previous

papers. Their applicabilities as cationic dye on Cashimilon F

(acrylic fiber) were also examined.

Department of Applied Chemistry, College of Engineering, University of Osaka Prefecture :

Mo,ur-U,nemachi, Sakaai-shi, Osaka, Japan

11.1.111111...1.l11r..r11//1e/111111/11..1Ie......1/1.Ir1.111.1111/r//////l/1.1..../...IIr Ir/11/1/.1..... /.

Kogyo Kagaku Zasshi 68, 1717--'l721 (1965)

Synthesis of Quinacridone

by Hisao NISHI, Yoshio NAGAI and Hiyoshi HASEGAWA

5, 12-Dihydro-quino-[2, '3-b] -acridine-7,14-dione (quina-cridone) (Ill)' was synthesized by the following method in

three steps,


i) Quino[2, 3-b]-acridine-6, 7, 13, 14- (5H, 12H)-tetrone (quinacridonequinone) ( II ) was prepared in 7476 % yields by cyclization of 2, 5-bis (2-carboxyrnilino)-1, 4-benzo-

quinone ( I ) in polyphosphoric acid at 130150°C for 1--3 hours.

ii) 1[ was reduced with polyphosphoric acid and tin powders at 130°C for 30 minutes to 5, 6, 12, 13-tetrahydro- quino-[2, 3-b]-acridine-7, 14-dione (6, 13-dihydro-quina-cridone) (iv). iii) N was oxidized with sod ium-nitrobenzene-m-sulfonate, and the product was purified by dissolving in sulfuric acid and precipitating with water. Ill was obtained as deep red

powders in 85 a yield for ii. When I was treated in polyphosphoric acid at 130°C for

1 hour and reduced with tin powders, 11 was obtained in a total yield of 82o by the same procedures.

Institute of Industrial Science, University of Tokyo : Azabu-Shinryudocho, Tokyo, Japan

s !111111 l1!lf 11i/t/tiii//111/11i1rflf/11t!!Fliiltll/!illrll111i/i1!l1t1t111tt/ti. t. !11/11111! iiff ll111i.ii.

Kogyo Kagaku Zasshi 68, 1721'-1725 (1965)

Synthesis of Titanate Resin Coatings

by Toshio TAKESHITA and Noriyuki MIYAUCHI

Three types of titanate resin were prepared. The 1st one was synthesized as follows: Tetrabutyl titanate (TBT) was reacted with polyhydric alcohol, and then titanate resin was synthesized by the reaction of the formed titanate with linseed oil fatty acids. The 2nd one was prepared as follows: C(CH2OH)4 was partially esterified with linseed oil fatty acids, and then the remained OH group was reacted with TBT. The 3rd one was obtained as follows: The linseed oil fatty acids semi ester of C (CH2OH)4 which

prepared above, was reacted with CH3COCH2COOC2Hs partial chelate of TBT, and then the remained OH group of the semi ester was reacted with BuO Group of the chelate. Drying properties and film properties of the titanate resins were studied. Some of the 3rd type resin which were pro duced by the reaction of linseed oil fatty acids di-ester of C (CH20H)4 with CH3COCH2COOC2Hs di-chelate of TBT had excellent properties. The film had Sword hardness of 30,

good flexibility, and excellent water resistance.

Faculty of Engineering, Kagoshima University : Karnoikecho 52, City Kagoshima, Japan

11.1/1I. 1141 ti i11F1t 1f 11Ff t11/1tfFrt/a1•rt///1111 {i 11 !111!1//II II II If111/i{/lift tf l{/iii {a.F1.11/11f1t111.


Synthesis of 2-(p-Vinylphenyl) propylene Oxide and its polymerization

by Chikahiko NAKASHIMA, Shigeo TANIMOTO

and Ryohei ODA*

p--Vinylacetophenone and trimethylsulfonium iodide in dimethylsulfoxide were mixed with potassium tert-butoxide in dimethylsulfoxide at 20~-25°C, under a nitrogen stream . The reaction mixture was stirred for 2 hr., and added to a large volume of water, and an organic layer was separated. This layer was distilled in vacuo to obtain 55$ 2-(p-vinylphenyl) propylene oxide (I) in 55 / yield, by 8689°C 4.5 mmHg. I was also obtained by Grinard reac-tion; namely, chloroacetone was added to p-vinylphenyl-magnesinm chloride irl tetrahydro#grart at 0°c, and th

reaction mixture was stirred for 12 2 hr., followed hydrolysis with 10 % NH4Cl aqueous solution. The organ

] layer was then poured dropwise into C2H5ONa in C2H5OH at

-5--0°C . Water and ether were added to this mixture , a the organic layer was distilled in vacuo to obtain I in 11 yield, by 83-86°C/3.5 mmHg.

I was polymerized in bulk at 70°C, using BPO as an initiator. The obtained polymer, having epoxy groups in a side chain, decomposed at 347°C, [v] =0.70 dlrg-' (in benzene , at 30°C).

The crosslinked resin was obtained by heating I at 180°C, or heating I with ethylenediamine or adipic acid,. These resins were hard and stable to acid and alkali, except l I2SO4. Also, I was an excellent adhesive for Al or glass.

* Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University : Kyoto, Japan

1.1./i/trtil.lirrl/!•r.rrrt!/.!!!l1111.l..1..a11111fi1.r/!.1!/1!111(.111.11il1t1r1111ftf/llir!!r!.!.lrrrl,

Kogyo Kagaku Zasshi 68, 1729^J1732 (1965)

Aqueous Solution Copolymerization of Vinylacetate

and Moleic Acid

by Kenichi HATTORI and Yoshiaki KOMEDA

A Copolymerization of maleic acid and vinylacetate in an aqueous solution had been generally considered to be difficult, but their new successful copolymerization has been reported in an authors' patent (JAPAN PATENT 413250, 1963).

An initial rate of copolymerization and an extent of final conversion are remarkably affected by a pH of an aqueous solution. The former decreases with increasing pH: the reason is considered to be a decomposition rate of an initiator

(K2S2O$-NaHSO3). The latter increases with an increase of a pH in the range from 1.2 to 4. 0, whereas decreases with an increase of a pH from f. 0 to 8.0. The maximum degree of final conversion is obtained at about pH 4. 0, which cor-responds to primary dissociation of maleic acid. The primarily dissociated maleic acid (mono basic) forms an intermolecular hydrogen bond and takes a planer resonating structure which will enhance the polymerizability of the monomer, and the hydrogen ion causes relatively little hydrolysis of vinyl-acetate at this pH: thus the maximum conversion is affected. Alternative copolymers are obtained at pH 2~.'6 and those rich in vinylacetate are obtained at pH 7-8. Monomer reactivity ratios of vinylacetate (M1) and mono basic maleic acid (M2) are determined:

r1=0.445±0.015 r2-0.00 ±0.015

Industrial Research Laboratories, Wakayama, Kao Soap Co. , Ltd.

13.34 Minalo-yukrrshubata, lVaka aina-shi, Japan

.Iilf 1fr 1111 /l1IIf{1t•!41!{i!{/1/i1/1111111ltili1i111i.IF 11111111111/ft1.r111.1.11.1.rrr...rlrt!llrtjj1/!1/

Kogyo Kagaku Zasshi 68, 1 732 -1734 (1965)

Relationships between Yield and Molecular Weight Distribution in Radical Oligomerization of Styrene

by Eishun TSUCHIDA and Isao SHINOHARA

The radical oligomerization of styrene in carbon tetra' chloride using a, rx'-azobisisobutyonitrile as an initiator under the condition, [CC14]/[Styrene] =5, at 80°C, was studied to obtain a rclationahip between yield and mo1+"


ilar weight distribution of the resulted oligostyrene. In a a range of 3•-70 $ of a conversion, it was found

that the shape of molecular weight distribution curves of tbese samples was very similar to that of normal distri-

ution and M~, JM,~ of all the samples was about 1.2.

Department of Applied Chemistry, Waseda University : Tolsuka-cho, Shinjuku-ku. Tokyo, Japan

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Kogyo Kagaku Zasshi 68, 1735 1 741 11965)

Elementary Reactions of Metal Alkyl in Anionic Polymerization. II. Reaction Model of n-Butyllithium

in the Initiation Step of Acrylonitrile Polymerization

by Nariyoshi KAWABATA* and Teiji TSURUTA**

Reaction mode of n-butyllithium with acrylonitrile and methacrylonitrile in hexane and tetrahydrof uran solution was investigated under the usual polymerization conditions. n-8utyllithium was consumed not only by the conjugate addition reaction with monomer, but also by nitrile addition and n-butane formation reactions. Acrylonitrile and methacrylonitrile were nearly equally reactive toward n-butyllithium in hexane, but methacrylonitrile was much less reactive in tetrahydrofuran,

* Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University : Kyoto, Japan

" Department of Synthetic Chemistry, Faculty of Engineering, University of Tokyo : Tokyo, Japan

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Kogyo Kagaku Zasshi 68, 1741-'1747 (1965)

Copolymerization of Ethylenimine and Cyclic Esters

by Tsutomu KAG/YA, Shizuo NARISAWA,

Kuniyoshi MANAGE and Kenichi WKUI

The copolymerization of ethylenimine and cyclic esters was carried out, and the structure of the produced copolymer was studied by infrared spectrum. The copolymer of ethyl-enimine and /3-propiolactone has the following structures which are strongly dependent of the dielectric constant of the reaction medium employed , and independent of the kinds of catalyst and the order of monomer addition .

f CH2CH2NHCOCH2CH2O-}- ( I ) -(-CH2CH2N*

COCH CH OH { } -E-CH2CH2NHCHSCH2COO* ill

r+~ -fCH2CHNH*

CH2CHaCOO N ) -(CII2CH2N}

ClI2CH2NHCOCII2C112011 ( V ) In the solvents with low dielectric constant

, acyl-oxygen fission of j-propiolactone takes place and the copolymer has

the elementary structures of I, II and V. While in the

Solvents with higher dielectric constant, alkyl-oxygen fission

Occurs and the copolymer has the ]II and N structures. A

nd, in the solvents with medium dielectric constant, the

COpolymer has all of these structures . In the copolymerization of ethylenimine and r -butyro-

hictone, or e-caprolactone , the copolymers have only the

structures resulting from acyl-oxygen fission of lactone , which are independent of the dielectric constant of the solvent employed. The role of the solvent causing the change of ring-fission of j9-lactone may be ascribed to the change of the distribution of electron density of the monomer by the specific solvation to the carbonyl bond of lactone .

While, no change of ring-fission takes place in r- and e-lactones.

Faculty of Engineering, Kyoto University : Kyolo, Japan .rfflrffrrff..fr.afl//trrr...err/rfr..rill.rrrlr...rl../fIr}!!.•rrrl!lie/.r•}

rllr}+rf}erlrra..frr..rr/.fry


Block Copolymerization with Trapped Radicals

by Yuji MINOURA and Yayoi OGATA

Acrylonitrile-styrene, vinylchloride-styrene and vinyl-chloride-methylmthacrylate block copolymer were obtained by employing trapped radicals in polyacrylonitrile or poly-vinylchloride which were formed by heterogeneous poly-merization with tri-n-butyl boron in air as an initiator . The trapped polymer radicals were activated by adding dimethylformamide as a solvent. Confirmation of block copolymers was carried out by solvent extraction , turbido-metry and elementary analysis. In block copolymerization , polyacrylonitrile trapped radical was more active than polyvinylchloride trapped radical. From results of kinetic studies, the mechanism of poly-merization was considered.

Department of Chemistry, Research Institute for Atomic Energy, Osaka City University : Minami-ogimachi, Kita-ku, Osaka, Japan f.1.r...rrfrrf•fllf.rrrrrffl/rarrrlfrtr...}.f/i/..lrfrllflrlflfrlr...fill.rffr//.rrfrlrr.rf/rr/a

f/l.f/rl.

Kogyo Kagaku Zasshi 68, 1752-'1756 (1965)

Synthesis of Polyamides Containing Disulfide Bonds

by Hiroaki TONAMI and Masatoshi IGUCHI

Linear polyamides containing disulfide bonds in their main chains were synthesized from acid chloride of dithiodiacetic acid or 3, 3'-dithiodipropionic acid and several diamines by an interfacial polycondensation method. Optium reaction conditions were searched for and properties of the resultant polymers were studied. It was found that acid chlorides with disulfides were so susceptible to an alkali that polycondensation reactions were accompanied with some decomposition, although polymers with fairly high molecular weight, of high crystallinity and spinnability were obtained when hexamethylenediamine was used as one component of the condensation. Intrinsic viscosities of polyhexame~hylenedithiodiacetoamide and poly-hexamethylene 3, 3'-dithiodipropioamide were 0.65 and 1. 00, and melting points were 167.4171 and l82~r87°C respect-ively. The chain repeat distances observed are 19.1 and 21.3A respectively, which are somewhat longer than those of ordinary polyamides obtained from corresponding alkylene-dicarboxylic acids. Copolyhexamethylene (dithiodiaceto-sebaco) amides with

intermediate properties between two home-polymers wire also synthesized. Disulfide bonds in main chains were fractured by adding

mercaptanes through an exchange reaction .

Department of Textile Engineering, Tokyo Institute of Technology: Ookayama, Meguro-ku, Tokyo, Japan .11r111r11/1//rift/r11/rlrf F•rf ruff rl•r1r!!rlf if •/trr111/11111111111/r11f1/ltl/111lf r}rrlf 1/1l rf ffllf/}}Lf


Kogyo Kagaku Zasshi 68, 1756--' 1761 (1965)

The Preparation and Thermal Degradation of Polyimide Containing Naphthalene Nucteus in its Main Chain

by Shun-ichiro NISHIZAKI

The new polyimides which contained six membered imide ring in their main chain were prepared by the condensation of naphthalene-1, 4, 5, 8-tetracarboxylic dianhydride with various primary aromatic diamines in dimethylacetamide . Primary aromatic diamines employed in this investigation were p- and m-phenylenediamine, benzidine, o-toluidine, 4, 4'- diaminodiphenylether, 4, 4'-diaminodiphenylsulfone and 4, 4'-diaminodiphenylmethane, while hexamethylenediamine

was used as an aliphatic diamine for a comparison. It was shown that these polyimides had the characteristic

absorption bands (v ) in 1712 1718 cm ' and 1675-1679 cm-' (N-aromatic substituted polyimides), and in 1705 and 1644 cm-' (N-aliphatic substituted). It was concluded from the results of IR spectra that polyimides were formed by intramolecular condensation of polyamidic acid.

Thermal stability of these polymers was studied by thermogravimetric analysis in air. N-aliphatic substituted

polyimide was rapidly degraded above 300°C, but N-aromatic substituted polyimides showed a good thermal stability and began to decompose above 400°C. It was concluded from IR spectra of the degraded polymer that >N-R bond of N--aliphatic subsfituted imide groupe was easily broken above 300c.

The Central Resrurch Lalrorrllorics, Milsuhishi Electric Corporation Amagasaki, Japan

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Kogyo Kagaku Zasshi 68, 1762-1765 (1965)

Crosslinking of Polyvinyl Alcohol Fiber with N-Methylol Acrylamide by Curing Method

by Yoshio NAKAMURA and Michiharu NEGISHI

In order to improve both shrink-proof in boiling water and elastic recovery of elongation of polyvinyl alcohol (PVA) fiber without formalization, the heat-treated PVA fiber was acrylamidomethylated by curing method and then cross-linked with alkali catalyst.

The PVA fiber was immersed in an aqueous solution containing N-methylolacrylamide (N-MAM) , acid catalyst (NH4C1 or CH3CHOONH4) and polymerization inhibitor (NaN02 or hydroquinone monomethylether), dried, cured and treated with NaOH solution containing Na2SO4. The acrylamidomethylation took place easily without producing insoluble N-MAM homopolymer by curing at 100.130°C for 10 min., the add-on being 0.090.15 mmole/g . When the acrylamidomethylated PVA fiber of add-on 0.08 mmole/g. was treated with 2 / NaOH solution containing 200 Na2S04 at 60°C for 15-v120 min., the degree of crosslinking was 0, 022ti0, 059 mmole/g. The shrink-proof in boiling water of the crosslinked fiber was improved excellently beyond 0, 03 mmole/g of the degree of crosslinking, being the same with conventianal vinylon fibers. Although the crosslinked fibers showed significant improve-ment in elastic recovery of elongation , particularly wet

recovery, as compared with the untreated or formalij

fibers, their tensile and knot strength and elongation de-

creased greatly with increase of the degree of crosslinkit, Th

eir decreases were lowered considerably adding poly

merization inhibitor in the curing process to prevent the

formation of insoluble N-MAM homopolymer.

Family of Engineering, Gumrna University : Kiryu-shi , Japan

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rN

Kogyo Kagaku Zosshi 68, 17661768 (1965)

Crosslinking of Polyvinyl Alcohol Fiber with N-Methylol

Acrylamide by Wet-heating Method under Pressure

by Yoshio NAKAMURA, Michiharu NEGISHI and Yukio TAKEKAWA

In the previous report, it was recognized that in the acrylamidomethylation of heat-treated polyvinyl alcohol

(PVA) fiber by curing method, addition of a polymerization inhibitor showed a considerable effect to retain the tensile

and knot strength of crosslinked fiber and also the fiber showed the shrink proof in boiling water and the excellent recovery of elongation, particularly wet recovery. Then, to obtain more improvement in tensile and knot strength, acrylamidomethylation of the heat--treated PVA fiber was carried out by wet-heating method under pressure ,

with an aqueous solution containing N-methylol acrylamide, acid catalyst (H2S04), coagulating agent ((NH4)2S04) and

polymerization inhibitor (hydroquinone monomethylether), and then the treated fiber was crosslinked with NaOH solution by the method given in the previous report. The PVA fiber was acrylamidomethylated easily without the formation of insobuble N-methylolacrylamide homo-

polymer and the optimum condition was N-methylol acryl-amide 2 /, H2SO40, 5/, (NH4)2SO4d5/, and hydroquinone monoethylether 0.3/ at 170°C for 60 min , and the extent of reaction was about 0.08 mmole/g. The crosslinked fiber showed excellent elastic recovery,

particularly wet recovery with little decrease of the tensile and knot strength as compared with the fiber prepared by curing method and showed good resistance in boiling water.

Faculty of Engineering, Gumma Universiiy : Kiryu-shi, Japan

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Preparation of Amphoteric Ion Exchange Fibers

by Hiroaki EGAWA

The present investigation was undertaken to prepare the amphoteric ion exchange fibers.

(1) By the phosphorylation of halogen-acetalized poly-vinyl alcohol fibers with phosphorus oxychloride or phos-phoric acid and urea, and then by the amination of these products with methylamine or ethylenediamine, favorable amphoteric ion exchange fibers having cation exchange capacities of 1.52.5 meq./g. and anion exchange capacities of 1.02.0 meq./g. could be prepared.

(2) By the hydrolysis of vinyl chloride-acrylonitrile copolymer fibers with aqueous sodium hydroxide, and then by the amination of these products with methylamine or ethylenediamine, satisfactory products exhibiting cation

Kogyo Kagaku Zasshi Vol. 68 No, 9 (1965) A 107

exchange capacities of 1.5 -3. 0 meq./g. and anion exchange capacities of 1.0-~2.0 meq./g. were obtained. The resulting

products by the above two methods had good physical pro-perties and good chemical stability.

Faculty of Engineering, Kumamoto University : Kurokami-machi, Kumamoto-sht, Japan

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Conditions for Preparing Vinylidene Chloride-Vinyl

Chloride latex with Nonionic Surfactants. I,

by Soichi MUROI

Conditions for preparing vinylidene chloride-vinyl chloride

latex with nonionic surfactants were investigated on a

laboratory scale. Nonionic surfactants, such as poly-

oxyethylene lauryl-, oleyl- and nonylphenyl ether with

various molar ratios of ethylene oxide were evaluated in

the emulsion polymerization, Thus, it was shown that

selecting the surfactants with proper molar ratio of ethylene

oxide and with proper hydrophobic group was of profound

importance to carry out a stable polymerization run . Of the tested surfactants, nonylphenol adducts with 30 to 50

molar ratios of ethylene oxide gave the most stable results . The initial rate of conversion increased in the order of the

surfactants with nonylphenyl-, oleyl- a-'d lauryl groups,

and the particle size of the latex decreased with increase

of molar ratios of ethylene oxide in the surfactants , when the polymerization runs were fairly stably carried out .

Pioneering Research Laboratories , Asahi Chemical Industry Co. , Ltd.: 27-36, 3-chome, Nakadai, Itabashi-ku , Tokyo, Japan

....Ia.1..rr.....Irrt/r...rrr/t1//...L.r•r.r.r.......Ia..lat.......r..rrrrr.....r.r.ra.r.rarl/./.araa.r...•

Kogyo Kagaku Zasshi 68, 1779 -1784 (1965)

Conditions for Preparing Vinylidene-Chloride-Vinyl

Chloride latex with Nonionic Surfactants. II.

by Soichi MUROI

Conditions for preparing vinylidene chloride-vinylchloride latex with nonylphenol adducts were investigated using 25-liter pilot plant equipment with an impeller shaped agitator , and the results were compared with those obtained in a

previous work. The important results were as follows; (1) time required to complete the emulsion polymerization decreased with an increase of the concentration of initiator and of molar ratios of ethylene oxide in the adducts up to 30 molar ratios, but did not depend upon the concentration of the adducts, (2) the emulsion polymerization was stably carried out using the adducts with 25 to 35 molar ratios of ethylene oxide the concentration of which , based on the monomers being from 5 to 6 f . The stability was the more affected by agitation speed, the more molar ratio of ethylene oxide the adducts contained , (3) particle size decreased with an increase of the concentration of the initiator and the adducts with more than 30 molar ratio of ethylene oxide , (4) it gave better results with the mixtures of the adducts, whose average molar ratio was 25 to 35 , than with a sort of the adduct .

Pioneering Research Laboratories, Asahi Chemical Industry : Co., Ltd.: 27-36, 3-chome, Nakadai, Itabashi-ku , Tokyo, Japan

1lllf/aarlf ftlliff/a/a1f..rrfal.frl/Ia..frfif •talirf/tlft1af 1111111x1. rr Lff/tltli l.l.. Y..Y YY.Y............


The Effect of Electrolytes on the Preparing Conditions

of Vinylidene Chloride-Vinyl Chloride latex with

Nonionic-Anionic Surfactant Mixtures

by Soichi MUR01

The preparing conditions of vinylidene chloride- vinyl

chloride latex with nonionic-anionic surfactant mixtures

were investigated in the absence and the presence of elect-

rolytes. Surfactant mixtures of nonylphenol adducts with

various molar ratios of ethylene oxide and two types of

anionic surfactants, sodium dodecylbenzene sulfonate and

sodium polyoxyethylene nonylphenyl sulfate of various mix-

ing ratios were evaluated in the emulsion polymerization.

Thus, it was found that the amount of coagulum formed

during the polymerization versus the mixing ratio exhibited

a maximum at near 1:1 mixing ratio in the absence of

electrolytes, but the amount of it decreased rapidly with an

increase of anionic surfactant in the presence of electrolyte,

and that the initial rate of conversion showed about inter

mediate values between the values for anionic and nonionic

surfactants according to the mixing ratio, but the diameter

of latex particles decreased rapidly with an increase of

anionic surfactant. A stable latex was obtained in the

presence of an anionic or nonionic surfactant. Furthermore, more stable latexes were obtained by adding a proper

amount of electrolyte in the presence of the mixture of the

anionic and the nonionic surfactants.

Pioneering Research Laboratories, Asahi Chemical Industry Co. , Ltd.: 27-36, 3-chome, Nakadai, Itabashi-ku, Tokyo, Japan

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A Study on the Mechanical Stability of Latex

by Soichi MUR01

Several factors which affect on the mechanical stability of vinylidene chloride- vinyl chloride latex were studied by, means of the measuring apparatus devised by Maron. In the preparation of the latices, sodium dodecyl benzene sulfonate, sodium polyoxyethylene nonylphenyl sulfate and

polyoxyethylene nonylphenyl ether were used as the sur-factants. It was shown that the mechanical stability varied with the type of the surfactants and the particle size, when the adsorption concentration of the surfactants on the surface of the latex particles was held constant, below the saturated adsorption concentration, but it did not vary above the saturation concentration regardless of the type of the surfactants and the particle size. Furthermore, it was found that the stability decreased rapidly with an increase of post-plastisizing degree of the dispersed poly-mer, and that surfactants and water soluble polymers could not satisfactorily stabilize post-plastisized latex, but that the copolymer latex containing acrylic acid (more than 2 wt. %) was stable.

Pioneering Research Laboratories, Asahi Chemical Industry Co., Ltd.: 27-36, 3-chome, Nakadai, Itabashi-ku, Tokyo, Japan

A lab Kogyo Kagaku Zasshi Vol. 68 No. 9 (1965)


A Study on the Foamability of Latex

by Soichi MUROI

The foamability of vinylidene chloride-vinyl chloride latices parepared with sodium dodecylbenzene sulfonate, sodium polyoxyethylene nonylphenyl sulfate or poly-oxyethylene nonylphenyl ether was measured by means of the apparatus devised by Tjutjunikow and Kassjanowa in connection with the mechanical stability and other factors. It was found that the foamability of the latex increased with an increase of adsorption concentration of the surfact-ants on the surface of the latex particles until full coverage was attained and varied with the type of the surfactants and particle size at the same coverage. Then, it was shown that a curve of the foamability versus surface tension was independent to particle size and that there was a linear relationship between the foamability and the mechanical stability, for a given surfactant.

Pioneering Research Laboratories, Asahi Chemical Industry Co. , Ltd.: 27-36, 3-chome, Nakadai, Itabashi-ku, Tokyo, Japan

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Kogyo Kagaku Zasshi 68, 1800^,1807 (1965)

A Study on the Freeze-Thaw Stability of Latex

by Soichi MUROI and Junji NOMURA

The freeze-thaw stability of polystyrene and polyvinyl acetate latices using cycles from -20°C to room temperature was studied. The important experimental results obtained were as follows; (1) the stabitity was markedly improved with an increase of adsorption conceetration of the surfactants on the surface of the latex particles up to the saturated concentration and varied considerably with types of the surfactants above the saturated concentration, (2) the stability of polyvinyl acetate latex increased with an increase of particle size, while that of polystyrene latex decreased slightly with increase of the particle size, (3) depression of Ts by means of external and internal plastisizing resulted in decrease of the stability, (4) an addition of hydroxyethyl cellulose or

polyvinyl alcohol at the initial stage of the emulsion polymeri-

zation improved the stability to a great extent, while ad-dition of those after the polymerization scarcely affected the stability, (5) the stability was greatly improved with an increase of the amount of copolymerized acrylic acid.

Pioneering Research Laboratories, Asahi Chemicol Industry Co. , Ltd.: 27-3b, 3-chome, Nakadai, Itabashi-ku, Tokyo, Japan

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NOTES


Thermal Cracking of Liquid Hydrocarbon by High Voltage Discharge

by Kenji NAGATA

In the thermal decomposition reaction of hydrocarbons, it is necessary to elucidate the mechanism the earlier reaction. For this purpose, high voltage discharge in liquid will be the best method to investigate. By high voltage discharge, it was found that the gaseous decomposition products were acetylene, methane, and hydrogen. The ethylene was proved to be produced by the decomposition of the high temperature acetylene by the secondary reaction after the high voltage discharging.

Resources Research Institute 188, Kotobuki-cho, Kawaguchi-shi, Saitama-ken, Japan


Synthesis of 2-Butanone-4-ol from Crotyl Alcohol

by Shinichi TSURUGI, Jun HAYASAKI and Masafumi SAKAI

2-Butanone-4-ol was obtained in a yield of 5055 % by direct oxidation of crotyl alcohol with 02 gas in a solution containing PdC12 and CuCl2. To identify the product, gas chromatography was used and the yield was calculated from the weight of the 2, 4-dinitrophenylhydrazone.

Sakai Kojo, Kyowa Hakko Co. Ltd. : 1-1 Takasu-cho, Sakai-shi, Osaka, Japan ......1.111. f L....,.., L.,.. r .............l.. .,...... r.. as a...,..., l.,.....,,..,, f, t / i, t•., t....,.l,.N

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