kogyo kagaku zasshi - jst

Kogyo Kagaku Zasshi

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

Vol. 73, No. 7, pp. 1255~1732 (1970)

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 present issue, written in Japanese by the respective authors. Readers are recommended toto refer to the figures, tables, formulae etc. from the original papers. Editor

ORIGINALS IN SYMPOSIUM " STRUCTURES AND PROPERTIES

OF HIGH POLYMERS "

„, .....

Kogyo Kagaku Zasshi 73, 1372--1375 (1970)

Crystallinity of Thermally Decomposed Polypropylene

by Osamu ISHIZUKA

Polypropylene specimen was thermally decomposed at 300°C and fractionated to thirteen fractions using various solvents.

The molecular weight dependence of various properties, the formation conditions of specific crystalline modification, the transformation between crystalline modifications and the solubility of crystals have been investigated on these frac-

tions mainly by differential thermal analysis, X-ray diffraction and infrared absorption spectroscopy.

It was found that r-modification could be obtained success- fully from the fractions having a molecular weight of less

than 2,000. However, if the crystallization was allowed to take place from a solution, a-modification was obtained.

Heat treatment was carried out at the temperatures between the melting points of two modifications, and it was observed that the a-modification still grow due to he secondary

crystallization by the heat treatment at a temperature lower than its melting point and, on the other hand, r-modifica-

tion was obtained only by the heat treatment at a temperature higher than the melting point of a-modification, namely, by fusing and then cooling slowly. Even if fused and then

crystallized, a-modification was obtained with a higher cooling rate. It was also found that the solution behavior

was different between a- and r-modifications even if they were obtained from the same fraction, and that r-modifica-

tion from a hexane-soluble fraction was no longer soluble in xylene at 97.5°C. This result seems to be applicable to

the quantitative determination of r-modification.

Faculty of Engineering, Yamagata University: Yonezawa, Japan

Kogyo Kagaku Zasshi 73, 1376'-1381 (1970)

X-Ray Small Angle Scattering of Bulk Crystallized Polytetramethylene Oxide

by Akira TAKAHASHI and Hiroshi KITAGAWA

Polytetramethylene oxide (polyoxatetramethylene glycol) samples with molecular weight ranging from 20,000 to

40,000 were prepared by cationic polymerization. Their

molecular weight distribution measured by sedimentation analysis was fairly narrow and the ratio of M„IMr, was found to be 1.07. Crystallization of one of the samples (M =20,000) was studied by the small angle X-ray scattering

and dilatometric methods. The degree of crystallinity, melting point and lamellae thickness, respectively, were determined as functions of crystallization temperature. The equilibrium melting temperature of polytetramethylene oxide was evaluated to be 56°C. The long spacings perpendicular to the lamellae increased with increasing crystallization temperature, i. e. , at 0°C, d=280 A and at 26°C, d=780 A. A stepwise increase in the thickness of the crystalline lamellae has been observed, however, the results obtined are not sufficient to reach any conclusion. The interfacial free energy for the crystalline lamellae evaluated from the obtained data was ca. 2000 cal/mol irrespective of the cry-stallization temperature.

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

Kogyo Kagaku Zasshi 73, 1381-1386 (1970)

Fiber-Formation Mechanism of Tussah Silk Fibroin

by Kiyoshi HIRABAYASHI*, Hiroshi ISHIKAWA*,

Nobutami KASAI** and Masao KAKUDO***

The fiber-formation mechanism of Tussah silk fibroin has been examined. The liquid silk in the silkgland has an a-helical conformation, whose content showed a decrease in the anterior division of the silkgland.

Experiments on mechanical denaturation of Tussah silk fibroin showed that the shear rate decreased with increasing fibroin concentration, increasing temperature of silk fibroin solution, and increasing Ca2+ concentration. Microscopic observation of the silkgland under crossed nicols indicated. that the fibroin molecules in the silkgland have no orientation, however, they abruptly orient at the spinneret part and then crystallize upon their passage through a thread-

press. Small-angle X-ray study of dried fibroin suggested the existence of a number of microvoids.

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

** Faculty of Engineering , Osaka University: Suita, Osaka, Japan *** Institute for Protein Research, Osaka University:

Kita-ku, Osaka, Japan

A76 Kogyo Kagaku Zasshi Vol. 73, No. 7 (1970)


Crystallite Distortion in Drawn Polyvinyl Alcohol Fibers

by Sadayoshi WATANABE and Yutaka NIHONGI

Vinylon fiver, composed of polyvinyl alcohol (PVA) or its acetal, is expected to have crystallite distortion, as the fiber undergoes large drawing in the process of manufacture. In this paper, the method of obtaining crystallite distortion 77 using X-ray diffraction has been discussed and the i values for drawn PVA fibers have been determined.

In drawn PVA fiber, X-ray line profile follows a nearly Cauchy-distribution, so that V can be obtained together with crystallite size e by the Hall equation, (91 • cos O)/A=11+

(77. sin 0)IA, where RI is the integral breadth of the line profile, 0 is the Bragg angle and A is the wave length. The crystallite size thus obtained showed a coincidence with that estimated by X-ray small-angle scattering. Crystallite distortion was found to increase with increasing draw ratio and was almost unchanged at draw ratios greater than 500%.

77 was 6.8 X 10-2 rad. at draw ratio of 500 %. Crystallite width also increased with increasing draw ratio due to crystallization, but decreased at draw ratios greater than 500 % depending on the breakup of crystallites.

Department of Applied Chemistry, Faculty of Engineering, Hokkaido University : Sapporo, Hokkaido, Japan

........

Kogyo Kagaku Zasshi 73, 1393-.1 398 (1970)

Crystallite Distortion in Vinylon Fibers under Stress

by Sadayoshi WATANABE and Yutaka NIHONGI

In the previous paper, it was shown that vinylon fiber has residual crystallite distortion caused by drawing in the

process of manufacture and distortion can be measured using X-ray diffraction. In this paper, crystallite distortion in vinylon fibers under stress has been measured and the fine structure of stretched vinylon fiber discussed.

It was found that under stress an additional distortion makes appearance besides residual distortion and is almost reduced to residual distortion on removal of the stress. In the stress range 0 to about 0.5 g/d, the additional distrotion increases with the stress and is produced to residual distor-tion upon stress relaxation. Over 0.5 g/d, the additional distortion no longer shows a linear increase upon stretch-ing and reduction upon stress relaxation.

It was deduced that the additional distortions are due to local bending of crystallites and irregularity in the parts of crystallites grown by stretching, which correspond to elastic deformation and retarded elastic deformation, respectively, of the fiber.

Department of Applied Chemistry, Faculty of Engineering, Hokkaido University : Sapporo, Hokkaido, Japan


Crystallization of Vinylidene Chloride-Vinyl Chloride

Copolymer

by Kensuke OKUDA, Reiho TAKABE,

Kazuhiro WATANABE, Minoru SUGITA, Tetsuya HOTTA and Mitsuo ASAHINA

The effect of melting conditions on the crystallization and stretching behaviors, isothermal crystallization, and strain-induced crystallization of vinylidene chloride-vinyl chloride

copolymer has been studied by means of the low tempera-ture X-ray diffraction technique, density measurement and a polarized microscope.

The isothermal crystallization of copolymer specimens which contain no crystal nucleus is concluded to be a homo-

geneous nucleation process with three-dimensional growth. The rate of crystallization, the growth-rate constant , the linear growth rate and the nucleation rate of this copolymer all have maxima near 80°C.

The deformation makes the copolymer to crystallize even at temperatures lower than a temperature at which no crys-tallization takes place in the absence of any deformation. The rate of crystallization in a strained state is much

greater than that in the isothermal crystallization without deformation at the same temperature. Type of crystal

gorwth depends on the ratio of deformation.

Tokyo Research Laboratory, Kureha Chemical Ind . Co. , Ltd. : Hyakunin-cho, Shinjukit-ku, Tokyo, Japan

Kogyo Kagaku Zasshi 73, 1402-.1 407 (1970)

Crystallization and Annealing of Melt Blended High and Low Density Polyethylene

by Masaru KUNIMURA, Toshio NAGASAWA and Sadao HOSHINO

The mechanical properties and density of a melt blend of high and low density polyethylenes (HDPE and LDPE) vary proportionally with the blend ratio. In order to investigate the relationship of these properties to the state of the poly-mer in the blend, the authors have attempted to study the crystallization mechanism and the effect of annealing of these blends by means of dilatometry and differential thermal analysis. Detailed studies were carried out in order to elucidate whether or not the cocrystal of HDPE and LDPE proposed by Clampitt was formed in the crystallization process. From a plot of the crystallization temperature as a function of melting points of both components, it was found that three types of crystallizaton mechanisms take place in this process, rather than the generation of the cocrystal. In addition , it was found that the third peak observed between the melting

point peaks of HDPE and LDPE in the DTA thermograms of the blends annealed under various conditions was not due to the cocrystal but to the melting of LDPE.

Consequently it is obvious that in the melt blends of HDPE and LDPE, both components exist separately depending on the blending conditions used which induce the proportionality between the blend ratio and mechanical properties .

Hirakata Plastics Laboratory, Ube Industries Ltd. : Nakamiyakita-machi, Hirakata, Osaka, Japan


Effects of Stereoregularity on Crystallinity of Polypropylene*

by Katsuhiro MAEDA** and Hisaaki KANETSUNA***

Effects of stereoregulariy on the crystallinity of polypro-

pylene (PP) have been studied by thermal analysis and X-ray diffraction.

Crystallizations of the melt (at 196°C for 1 hour) were carried out both isothermally (at 90-155°C) and by cooling down to room temperature at various rates. In evety case

Kogyo Kagaku Zasshi Vol. 73, No. 7 (1970) A77

the melting point (the temperature of peak I ) of the crystals from the toluene insoluble fraction (TI) was higher

than that of the crystals from the toluene soluble-n-heptane insoluble fractions (TS). Peak II ' was observed at higher

temperature than that of peak I on samples from TS, which were crystallized isothermally at 90-110°C and then cooling

rate greater than 2°C/min. ; no such peak was observed on samples from TI. It seems that partial melting and recrys-

tallization by annealing during measurement took place easily on samples from TS in comparison with those from TI , and

that peak jj ', which was more stable than peak I , appeared due to the recrystallized structure.

Recrystallization and reorganization by annealing (120°C) took place on quenched samples from HS, TS and TI , and so peak ni was observed (at about 130°C) in the thermo-

grams. The height of peak II from TS samples are higher than that from TI samples and lower than that from HS samples. However, peak 1[ was not observed in the samples from HS, TS and TI, which were crystallized by slow cooling at a cooling rate of 1-1/3°C/min . On the other hand, a peak ill was appeared at 153-155°C in the these samples. The r-form of PP was obtained from HS by cool-ing at 0.1°C/min and in this process an endothermic peak was found at about 153°C.

Thermal Analysis on Crystallinity of Polypropylene. I. ** Toshiba Research and Development Center, Precision Engineering

Research Center : Komukai Toshiba-cho, Kawasaki, Japan *** Research Institute for Polymers and Textiles :

Sawatari, Kanagawa-ku, Yokohama, Japan


Effects of Molecular Weight on Isothermal Crystallization

of Fractionated Polypropylene*

by Katsuhiro MAEDA** and Hisaaki KANETSUNA***

Effects of molecular weight on the isothermal crystalliza-tion of fractionated polypropylene (PP) have been studied by thermal analysis. PP was extracted with the same solvent as that used by Natta. The toluene insoluble frac-tion (TI) was extracted with xylene in a nitrogen atmo-sphere for 4 hours after isothermal crystallization at 155°C for 120 hours. It was assured that the crystals from the xylene insoluble fraction (XI) were more stable than those from TI.

The obtained results are summarized below. 1) It seems that the melting point of crystals from the xylene soluble and toluene insoluble fraction (XS) is lower than those from XI and higher than those from the toluene soluble and n-heptane insoluble fraction (TS) , although the latter two fractions have the same molecular weight. 2) The highest equilibrium melting point Tm° of 232±2°C was obtained for crystals form XI. 3) Tra° and the melting point depend on the molecular weight of fractions. 4) The main peak in the thermograms was split into double peaks due to iso-thermal crystallization above 155°C. 5) Isothermal crytsal-lization kinetics was investigated in the temperature range from 120 to 130°C. 6) The half time t1,2 was dependent on the molecular weight of fractions. t112 of XS was found to be longer than that of XI and shorter than that of TS , although the latter two fractions have the same molecular weight. 7) The interfacial energy of PP crystals calculated

from the plot of ln (4,2)-1 against Tni°21T,(Tm° —Te)2 was in the order of 6.2-15.5 erg/cm2.

* Thermal Analysis on Crystallinity of Polypropylene . II. *5 Toshiba Research and Development Center, Precision Engineering

Research Center : Komukai Toshiba-cho, Kawasaki, Japan *** Research Institute for Polymers and Textiles: Sawatari, Kanagawa-ku, Yokohama, Japan


Polymer Crystals Formed from Solution under

Shearing-Stress

by Kazuo MONOBE, Yasuo FUJIWARA and Yuhiko YAMASHITA

Crystallization of polyethylene, isotactic-polypropylene , iso-tactic-polybutene-1, polyoxymethylene and polyvinylalcohol

from solution under shearing stress has been investigated . From the bright and dark field electron microscopic observa-tions, the electron diffraction study and the properties of the resulting fibrous crystals, the authors demonstrated that they consist of the central threads with an extended chain character and the lamellae with a folded chain character nucleated on the threads. In order to gain a deep insight into the structure of the lamellar parts, the long periods detected with small angle X-ray scattering and the lamellar thickness measured on the electron micrograph were studied as a function of crystallization temperatures. However, the fibrous crystals of polyvinylalcohol differ from the other

polymers in morphology and seem to consist of only extended chain crystals which contain some disorder parts. The thermal and mechanical properties for the macroscopic ori-ented crystals specimen reflected the fi brous structures. In

particular, the authors obtained the value of 237 kg/mm2 as Young's modulous parallel to the fiber axes of polyethylene specimen. Fusion curves of the same specimen showed the melting peak of 138°C, the superheating up to 150°C and the enthalpy of fusion of 63 cal/g, at 10°C/min of heating rate. Some crystallization behaviors characteristic to the stress-induced crystallization from solution were explained by the decrease of free energy of critical nucleus formation based on the decrease of chain conformational entropy under stress.

Department of Industrial Chemistry, School of Engineering, Okayama University : Tsushima, Okayama, Jayan


Thermal Degradation of Cellulose Phosphate and

NH4H2PO4 Containing Cellulose*

by Norihiro INAGAKI and Kakuji KATSUURA**

A kinetic study on the thermal degradation of cellulose

phosphate ( I ) and NH4H2PO4 containing cellulose ( II ) has been made. Upon application of various methods to the

thermogravimetric data, Ozawa's method with Doyle's cor-rection was found to be the most suitable one for the degradation of these samples. Based on kinetic analysis, it was found that in the thermal degradation of I was two stages process. On the other hand, the degradation of depended on the phosphorus content, i. e., the degradation occurred in two stages for the lower phosphorus content sample, and in three stages for the higher one. The energy


of activation for I was generally larger than that for ir These results show that the degradation of I and H differ in kinetics. The second stage degradation, occurring in the residue range of 90%, to 50%2, was the principal reaction for

. The reaction order n2 of the second stage for H in-creased with phosphorus content, but both the activation energy and the pre-exponential factor of the Arrhenius equations were independent of the phosphorus content. The increase in n2 with phosphorus content shows that the rate of degradation, namely, the rate of diffusion of volatile materials through the carbonized phase of the residues, decreases with phosphorus content. This phenomenan was supported by micrographic photographs for a series of I with various phophorus contents, heated up to the second stage.

* Studies on Thermal Degradation of Phosphorus Containing Polymers. II.

** Faculty of Engineering, Shizuoka University: Johoku, Hamamatsu, Shizuoka, Japan

Kogyo Kagaku Zasshi 73, 1438—'1443 (1970)

Synthesis and Thermal Stability of Mixed Amine

Complexes of Metal Tetracarboxylic Diimidates*

by Nobumasa HOJO, Hirofusa SHIRAI and Akira SUZUKI**

The preparation and thermal stability of a series of ali-

phatic amine complexes of bivalent transition metal tetra-carboxylic diimidates have been investigated. The prepara-tion of amine complexes of metal pyromellitdiimidate (PMDI) and 3, 3', 4, 4'-benzophenone tetracarboxylic diiminate (BTDI) was carried out in dimethylformamide (DMF), and that of metal 1, 2, 3, 4-cyclopentane tetracarboxylic diimidate

(CPDI) was carried out in ethanol. The infrared spectra of a series of complexes were examined in the range from 4000 to 200 cm-1. The complexes of copper (10, nickel ( 10,

zinc (10 and cadmium( ) showed a single sharp absorption band in the vicinity to 3300 cm-1, which was assigned to be the NH stretching frequency. In free ammonia, this band was osberved at 3414 cm-1. This blue shift in frequency is due to the coordination of the amine with the metal atom, resulting in the formation of a highly covalent N-,M bond. The magnitude of this blue shift in PMDI metal complexes decreased in the order of nickel( H ) >copper( H ) >zinc( IL >

cadmium ( H ). The IR spectrum of the cobalt ( H ) complex showed a doublet in this region. The band due to the carbonyl stretching frequency in the metal free ligand occurred at about 1720 cm-', while in the case of complexes it showed a shift in the range from 1680 cm-1 to 1600 cm-1. In the case of complexes, the increased electron density reached a saturation point beyond a single bond. In PMDI complexes, the stretching C=0 frequency, v0,0, decreased in the order copper ( H ) >zinc( 11 ) >cadmium( H ) >nickel( H )

> cobalt ( II ), and the heat stability of the complexes de-creased in the order zinc ( H ) >cadmium( ft ) >nickel( H ) >

copper( lir ) >cobalt ( IL ). The molecular weight of PMDI copper( H ) complex determined by Rast's method was found

to be above 2000. All complexes showed crystalline X-ray

partterns and were insoluble in the conventional solvents.

* Studies on Thermally Stable Polymers. III. ** Faculty of Textyle Science and Technology, Shinshu University:

Ueda, Nagano, Japan

Kogyo Kagaku Zasshi 73, 1444-'1449 (1970)

Changes in Mechanical Properties of ABS Resin on

Thermal Aging*

by Kimiaki KABUKI**

The previous report was on the change of mechanical

properties and the mechanism of thermooxidative degrada-tion of ABS resin in a Gear oven at 70-90°C.

In this work, the aging properties have been studied in accordance with the thermal aging mechanism. During thermal aging, two stages in the oxidative reaction were easily distinguished by an analysis of the degradation. The

product from the first stage, the initiation stage, which involved mainly the formation of hydroperoxides induced by radical formation, had greatly reduced elongation and impact strength, whereas the product from the subsequent second. stage, which is initiated by the decomposition of the hydro-

peroxides and induced chaincarrier reactions, had lower impact and tensile strengths.

When aging time was long, there was no change in hue, and the main wave-length of light absorption, Ad, was in the range 570-590 ma, that is the resin had a yellow or yellowish brown color. With the advance of thermooxida-tion, this color (saturation) became deeper and the bright-ness became duller. The discoloration corresponded to an increase in the oxidation products and a degradation in the material properties.

* Study on Degradation and the Stabilization of ABS Resin. III. ** The Material Research Laboratory, Tokyoshibaura Electric Co.,

Ltd. : Komukai-toshiba, Kawasaki-shi, Kanagawa, Japan

Kogyo Kagaku Zasshi 73, 1450-1 454 (1970)

Photoconduction of Polyrhodanines*

by Ryo HIROHASHI, Yasushi HISHIKI

and Masaaki DOHI**

Polyrhodanines were synthesized by the polycondensation reaction of p-phenylene bisrhodanine, 4, 4'-diphenylene bis-rhodanine, 1, 5-naphthalene bisrhodanine, 4, 4'-diphenylme-thane bisrhodanine or hexamethylene bisrhodanine with terephthal aldehyde.

Polyrhodanines have a photoconductive character in the region from visible to near infrared. For the investigation of photoconduction, a surface-type cell was employed to avoid the effect of space charge which was observed in the case of a sandwich-type cell.

Dependences of dark- and photo-currents on electrical field strength showed linear relationships. The ratio of photo-current to dark current increased with increasing applied

potential; polyrhodanine containing hexamethylene showed the largest ratio of about 3.6 x 103.

The light intensity (L) and spectral dependence were ob-served for the photo-current (In) . The values of n in the expression /pocLn were from 0.86 to 2.59. For all the poly-rhodanines, peak in the photo-current response curves were found near 554 mg. The long wavelength edges in photo-conduction were observed at 1.24 At for a polymer containing hexamethylene, at 1.07 ju for a polymer containing naphtha-lene and at 0.90 g for the other polyrhodanines.

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

Japan



Photoconduction of Polyoxazoles*

by Ryo HIROHASHI, Yasushi HISHIKI and Shozou ISHIKAWA**

Polyoxazoles were synthesized by the polycondensation reaction of 2, 6-di (p-aminophenyl)benzbisoxazol with either terephthal aldehyde (PA) , isophthal aldehyde (PB) , glyoxale (PC) , terephthaloyl chloride (PD) , isophthaloyl chloride (PE) , p-xylylene dibromide (PE) or chloroanil (PG). In order to investigate of phtoconduction at 10-6 Torr, a surface-type cell was employed to avoid the effect of space charge which was observed in the case of a sandwich-type cell.

The polyoxazoles PE and PO showed the largest photo-conductions of 4.66 x 10-11 A and 6 .90 x 10-1' A, respectively. The dark-current (Id) and photo-current (In) dependence on the electrical field strength ( V) showed a linear relation-ship. The values of a and 8 in the expressions Id CC k V" and

I pock VP were found to be smaller than one except those for PG. The light intensity (L) and spectral dependences for the photo-current were observed. The values of n in the expression /pocLn for the different polyoxazoles were between 0.68 and 2.60. The peak wave-length in the photo-current for all the polyoxazoles was shorter than 398 ma.

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


Relation between Electrostatic Charge and Number of

Bonding Units on Copolymer

by Isao SHINOHARA, Harunobu TSUIKI and Eishun TSUCHIDA

The electrostatic charges of the copolymer composed of two monomers (M1 and M2), which bring about different signs of charges on the copolymer, are decided by the chargeability of one component (M1) when M1 is above a certain value. However, when the content of the other component (M2) increases, the chargeability of the copolymer becomes to be decided by M2. These phenomena can be interpreted by the formation of new energy levels on the bonding between M1 and M2.

Polystyrene, which is charged positive, and poly-E-methyl methacrylate), which is charged negative , have the same

chargeabilities, therefore, the bondings between styrene and methyl methacrylate in the copolymer (St-MMA) are con-sidered not to contribute to the charge formation . On the basis of this assumption, the saturated charges on the St-MMA copolmer are calculated from the number of the bonding between St and MMA. The measured curves of copolymer composition vs. saturated charges of triboelectri-city on the polymer surface is in good agreement with the calculated one.

These phenomena were also observed in the case of other copolymers, e. g. MMA-MAn, St-VAc or St-AAm. It can be concluded that the charge transfer occured through the bonds between different monomers (M1 and M2) and the new energy levels are formed.

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


Effect of Temperature on Electrification of Copolymers

by lsao SHINOHARA, Harunobu TSUIKI

and Eishun TSUCHIDA

To study quantitatively the contact electrification of dif-ferent polymers and its relationship with their chemical structure, the effect of temperature on the electrostatic charge has been investigated. In the case of polyacrylamide

(PAAm) or methyl methacrylate (MMA) -maleic anhydride (MAn) copolymer, the charge decay was comparatively large and the maximum charge decreased with increasing tempera-ture. While, in the case of polystyrene (PSt), PMMA or St-MMA copolymer, the charge decay was very small and the maximum charge was not influenced by temperature. The fact that the electrostatic charge on the polymers at the glass transition temperatures did not show the same behavior as the bulk conductivity implies that electricfica-tion can be considered to be merely a surface phenomenon like sarface conductivity.

The saturated charge is proportional to the charge decay constant and hence must be related to the mechanism of charge decay, i. e. of charge transfer. Assuming that the trap level takes place in the electrification and that the activation energy of charge decay is the activation energy of charge transfer, the depth of trap level was estimated as 0.1-0.5 eV. Activation energies of conductivity have higher values in the range 0.5-1.5 eV and are inversely related to the activation energies of charge decay. The

effect of temperature on electrostatic charge has been dis-cussed in relation to the depth of trap level and examined with the help of a contact electrification.

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


Sorption of Gases in Polyethylene Films

by Keio T01*, Takashi KAMINAGA**

and Taneki TOKUDA*

The sorption of gases in polyethylene films has been measured by using a newly-devised apparatus, which gives the sorption rate curves from the initial to the equilibrium state. A marked difference between the Ziegler-catalized poly-

ethylene film and the high pressure polyethylene film ap-

peared in the sorption rate curves. This indicates that there is difference in the properties of the surface and the amor-

phous phase of these polymers. By analysis of sorption curves for several gases absorbed in a Ziegler-catalized

polyethylene film, it was shown that the sorption rate, as well as the equillibrium solubilities, can be explained by the dual-mode sorption mechanism proposed by W. R. Vieth et al.

The results could be quantitatively explained by postulat-ing two concurrent mechanisms for sorption; ordinary dis-solution and adsorption.

* Department of Chemistry, Faculty of Science, Tokyo Metropolitan University : Setagaya, Tokyo, Japan

** Chiba Laboratory, Nissan Chemical Industries, Co. , Ltd. Goi Minamikaigan, Ichihara, Chiba, Japan



Rheological Treatment of Rate of Setting of Curing Type Adhesives*

by Kisou KANAMARU, Shoichiro YANO and Norio KOSUGE**

The tensile rupture strength f(t) of adhesive joints made of organic polymers as the adhesives (AS) and metal (steel) as the adherent (AH) during adhesive setting is given by

f(t) =fm(t) — E(t) • r (t) (1) where fin(t) and E(t) are the cohesive stress and modulus, respectively, and r (t) is the differential internal strain developed in the joint at time t.

In the present paper, instead of thermoplastic polymers which have been considered as the adhesives in the previous paper (Kolloid-Z. u. Z. Polymere, 209, 151 (1966)), curing type (thermosetting) polymer adhesives are considered and the mechanism of the rate of setting of such resins is

theologically treated. It is assumed that both the non-relaxation and relaxation terms Eco and E(0) respectively in the equation

E(t) =Ec0-1- E (0) e-t/r (2) increase with time t as the bond formation proceeds due to the same molecular mechanism (with the same time para-meter 7.2) as in the increase of fm(t) and r(t) participating, and E(t) is thus approximately given by

E(t) =E0+ Eco(1—e-t/r2) + [EP- E! (1—e-t/r2)].e-t/ri (3)

non-relaxation term relaxation term The function thus derived from (1), (2), (3) and the ap-

proximations formerly considered fm (t) °+f,, (1—e-t/r2) (4)

and r (t) =r „c> (1 —e-tir2) (5) is gigen by

f(t) = f + —ni[Eo+E.(1—e-t/r2)]ro. n2 n2

—n1 [EI 0 E.I.! (1 — erntir2)] e-t/vin} (1— e-t/r2) (6) where the stress concentration factor n2 due to the presence of weak spots in the adhesive layer and ni due to the dif-ferential thermal contraction are considered, as has been done in the previous paper.

From the function obtained (Eq. (6)), the extremum tensile rupture strength fext was derived, when df/dt=0 and as-suming ri< r2 for the rheological condition of time period of experimental observation ; it was thus estimated that the function f(t) in a joint system made of a curing type poly-mer adhesive has a maximum (d2f/dt2 is negative) at a definite time t, below but comparable with r2.

The experimental f vs t curves obtained for the joint system steel (AH)-bisphenol A triethylenetetramine type epoxy resin adhesive at various temperatures were found to have maximum and results were interpreted in terms of the f(t) function derived (Eq. (6)).

Rate of Setting of Adhesive Joints Made of Curing Type Adhesives. I.

** The College of Science and Technology, Nihon University: Kandasurugadai, Chiyoda-ku, Tokyo, Japan


Mechanism of Rate of Setting of Bisphenol A - Diamine Type Adhesives*

by Shoichiro YANO, Norio KOSUGE and Kisou KANAMARU**

As typical curing type adhesive polymers, some bisphenol A epoxy resins cured with different molecular species of

diamines as hardners were used. The specific volume v and the modulus G of the resins and also the rupture strength f of the joint (butt joint) were measured as func-tion of time t in the course of the setting process of the

resins. The effect of the change of the molecular structure, espe-cially the chain length of the cross-linking chain section caused by the use of different diamine species, upon the rates of change of G and v of the resins and of f of the joints were studied.

Generally, increases in the modulus z1G and the volume contraction zlv with time proceeded as a typical retardation process with an empirical retardation time -r2 expressed by the following empirical expressions :

4G(t) = zIGa,(1e-t/r2) (1) and 4v(t) = z1v,, (1—e-t/r2) (2)

where 4G(t) =G(t) 4v (t) = v0— v(t) and 41),)=Vo—v. In view of the approximations carried out in deriving f(t)

in the preceding paper, the bisphenol A type epoxy resin adhesives used in this work are classified according to the molecular structure of the diamines used as hardners, that is a) the . densely cross-linked type obtained upon curing with diamines having small numbers of methylene groups

(ethylene- and hexamethylenediamines), and b) the loosely cross-linked type obtained upon hardening with diamines having large numbers of -CH2- groups (decamethylenedi-amine). The functions 4G(t) and 4v(t) obtained with the type a) resin follow approximately the expressions (1) and (2), respectively, and nearly the same apparent activation energies about 10 kcal/rnol) were obtained from the temperature dependence of the values of the empirical retardation time

7'2 of the above two retardation processes. The type of resins generally give a function f(t) having a maximum, as will be anticipated looking at the approximate f(t) developed in the preceding paper (Eq. (6)).

Compared with the type a) resins, the type b) resins show generally a typical increasing type f(t) without a maximum expressed by the form

f(t) L (1—e-t/r2) (3) This exrpession is to be anticipated at least qualitatively

considering the approximate f(t) derived in the preceding paper, in view of lower experimental values of G,,, rco and Tg (or accordingly, a larger contribution made by the relaxation term El; - Eci.! to the total modulus E(t)), for this type of resins.

* Rate of Setting of Adhesive Joints Made of Curing Type Adhesives. IL

** The College of Science and Technology, Nihon University: Kandasurugadai, Chiyoda-ku, Tokyo, Japan



Studies on Molecular Orientation by Spectropolarimetry

by Rempei GOTOH*, Noriyuki KIMURA**

and Soichi HAYASHI**

It has been shown that anisotropic absorption or dichroism due to molecular orientation can be discussed in terms of optical rotation recorded with a spectropolarimeter. When a polyvinyl chloride film containing anthracene was stret-ched, so-called optical rotatory dispersion curves were obtained at various elongations corresponding to the absorp-tion spectrum of anthracene.

The optical ratatory power a° at respective frequencies is related to the optical densities, A11 and AI, parallel and

perpendicular, respecitively, to the direction of stretching, as follows :

2 log (tan (45°— a)} = — A ±F-2-.D, (1) where D is the "dichroic difference".

Taking 0 as an average angle between the stretching di-rection and the transition moment of the absorption band , the orientation function F is given by the relation,

1 A11—A.1 F = —(3 cos20— 1) =•(2) 2 A u +2A1

The orientation function of polyvinyl chloride was obtained by using polarized infrared spectroscopy and compared with that of anthracene at respective elongations.

Kyoto Sangyo University : Kamigamo, Kyoto, Japan Institute for Chemical Research, Kyoto University:

Uji, Kyoto, Japan

Kogyo Kagaku Zasshi 73, 1485--)1488 (1970)

a*-Axis and c-Axis Mixed Orientatation of Isotactic Polypropylene and its Mechanism

by Hiroshi AWAYA

The structural changes taking place in isotactic polypro-

pylene during press deformation at various temperatures below the melting point have been studied by means of X-

ray diffraction analysis and differential thermal analysis. It was observed that the structural changes occurring in

the polymer in the course of press deformation depended on the processing method used for preparation of the original sheet for specimets. That is, when the original sheet was

prepared by quenching, the structural formation of the press-deformed specimen therefrom was found to consist of c-axis oriented crystallites in the flow direction and a*-axis oriented crystallites. In this case, the thermogram always showed two or more end thermic peaks. On the other hand, when the original sheet was prepared by gradual cooling, the press-deformed specimen therefrom indicated b-axis orientation only in the thickness direction. It this case, the thermogram mostly showed a single endothermic peak. Therefore, the thickness of a*-axis oriented crystallites is thought to be smaller than that of c-axis oriented crystal-lites. Also, the mechanism of mixed orientation has been studied.

The mixed orientation seems to have been caused by an epitaxial lamination of a*-axis oriented crystallites over c-axis oriented crystallites.

Research Laboratory, Tokuyama Soda Co., Ltd. : Mikage-cho, Tokuyama, Japan


Molecular Orientation Behaviors in Polyvinylalcohol Films Studied by the Fluorescence Method

by Yoshihiko ONOGI, Ken-ichi KAWAKAMI and Yasunori NISHIJIMA

The orientation behaviors of poly (vinyl alcohol) (PVA) films have been studied by the fluorescence method during uniaxial and biaxial stretchings. From a comparison with the orientation behavior of fluorescent polymers containing

polyene segments prepared by the thermal dehydration of PVA, a stilbene derivative fluorescent dye (Whitex RP) was chosen as the probe. The orientation patterns of polymer chains in non-crystalline regions in stretched PVA films were thus determined from the angular distribution of the

polarized component of the fluorescence intensity. In the case of uniaxial stretching, the observed orientation pattern indicated the presence of a highly oriented component in the direction of the stretching axis together with a component oriented in the direction perpendicular to the axis. This type of orientation cannot be treated by the simple affine transformation mechanism. As for the biaxial stretchings, there were notable differences between the successive and simultaneous biaxial stretchings. The degrees of orienta-tion were also measured by means of dichroism and bire-fringence and these data were compared with the results obtained by the fluorescence method. The mechanical ani-sotropy of the biaxially stretched films was also measured and discussed.

Department of Polymer Chemistry, Kyoto University: Sakyo-ku, Kyoto, Japan

,,,,, ..... ........... ...... ..••.•,,,o..•••...•.+. .........


Simultaneous Biaxial Stretching of Poly(ethylene

terephthalate) Film and Its Thermal Contraction

by Saburo OKAJIMA, Yuzo YAMAMOTO and Hiroshi TANAKA

Biaxially oriented films were prepared from undrawn

poly (ethylene terephthalate) film by stretching biaxially in one step to vA=17 (VA is the degree of stretching in terms of area) mainly at 80°C. The films thus obtained were thermally contracted at temperatures between 80 and 120°C, and the change in fine structure due to the stretching and shrinking were studied by means of optical and X-ray dif-fraction method.

Birefringence —45 of the film relative to the normal of the film surface increased gradually with vA, excepting a steep increase around vA =6-7. The X-ray diffraction

pattern, which was of paracrystalline nature indicated the onset of (100) selective uniplanar orientation at this values of vA. It was concluded, therefore, that this steep increase in —zInss was due to the benzene ring orientation parallel to the film surface. The films with vA<7 shrank nearly to the original area, when —4n fell to zero or had a small negative value, while those with vA>7 shrank only slightly, exhibiting a slight decrease in —zlnss. At the same time the films with vA<7 lost the selective uniplanar


orientation, which was, however, preserved by the films

with vA >7. Uniaxially stretched films shrunk under the

same condition preserved the c-axis orientation when the

degree of stretching v was larger than 2.8, while the

c-axis orientation changed into a-axis orientation when v

was smaller than 2. This transition zone is in good accor-

dance with the vA112--= 7112=2.7 of the above mentioned tran-

sition zone of the biaxially stretched films.

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

,,,,,,,,,,,,,,,,,,,,, ,,,, •-•„„•-• ,,,,,,, ,,,,,,,, .... ,,,,,,,,, ,,,,, ,,

Kogyo Kagaku Zasshi 73, 1499---1504 (1970)

Change with Draw Ratio in Fine Structure of Pre-treated 6-Nylon Fiber and Its Mechanical Properties

by Minoru HASHIMOTO and Toshio KUNUGI

The change with draw ratio in the fine structure of pre-treated 6-nylon fiber has been investigated by measuring crystallinities, crystallite sizes and optical orientation factors

(f0). The mutual relationships of these factors with such mechanical properties as static initial modulus, dynamic modulus, loss modulus and tan 8 have been disscussed.

From the investigation of the effect of fine structure on the static initial modulus and dynamic modulus, the follow-ing results were obtained : —

(1) The change in crystallinity was slight, and its effect on the moduli can be almost neglected.

(2) The optical orientation factor influenced the moduli more remarkably than the other two factors, and the moduli increased rapidly from f0=0.5 regardless of the treatment. In such high orientated specimens, the increase in modulus in also very dependent on the intertwining of molecular chains and structural stabilization.

(3) Although the static intial modulus and dynamic mo-dulus increased with drawing, tan 8 showed the maximum value at draw ratio 1.6. The maximum arises in the region between the structure with rubber like elasticity (undrawn specimen) and that with energy elasticity caused by a strong interaction between molecular chains resulting at high draw ratio.

(4) The effect due to crystallite size is observed at high orientation, and there is a tendency for the moduli to in-crease as the crystallites become smaller and numerous.

Faculty of Engineering, Yamanashi University : Kofu-shi, Japan

Kogyo Kagaku Zasshi 73, 1504—,1509 (1970)

The Deformation in Compression of Biaxially Oriented

6,10-Nylon

by Masataka KUROKAWA, Takashi KONISHI, Fumio TAKI and Ryosuke KAMEI

The deformation bands of biaxially oriented 6, 10-nylon filament which is compressed perpendicular to the chain direction with a light and electron microscopes has been investigated. On the surface of cross section of the specimen compressed

normal to the (010) planes, two families of band are observed which are inclined to rolled surfaces at about 40°C. On the other hand, the specimen compressed parallel to the (010) planes shows the buckling type of deformation caused by formation of kink bands. The orientation of crystallographic

planes will be rotated by the formation of these kink bands. The specimen compressed normal to the (010) planes at

180°C shows the terraced planes caused by longituidal shifts on the end surfaces. The shifts seem to be caused by the formation of deformation bands which are observed in the compressed planes.

The electron-microscopic observations of these local de-formation are reported.

Department of Textile Science, Kyoto University of Art Industry and Textile Fibers : Matsugasaki, Sakyo-ku, Kyoto, Japan

•.,„ ........... .•••. ........ ..... . ... .....


Structures and Properties of Chlorinated trans- and cis-1,4-Polybutadienes

by Masatami TAKEDA, Kazuyoshi IIMURA and Ryuichi ENDO

The local conformations of chlorinated trans- and cis-1, 4-

polybutadienes in solid state and in solution were studied by infrared spectroscopy, and the conformations were dis-cussed basing upon the structures of rotational isomers of 2, 3-dichlorobutane and of 2, 5-dichlorohexane ; the former represents a model compound for the structural unit of the chlorinated part and the latter is a model for the ethylenic

part in the chlorinated polymers. In the solid state, the population of the extended trans

form is somewhat dominant in the chlorinated part of both the chlorinated polymers. The carbon chain in the ethylenic

part of chlorinated trans-1,4-polybutadiene takes mostly trans-conformation, however, gauche conformation is fairly common in the case of chlorinated cis-1, 4-polybutadiene.

Solvent effects on conformational change in the chlorinated

parts of these chlorinated polymers were different from each other. It was found that a correlaion exists between this conformational change in the chlorinated part and the solvent effect on the conformational parameter in solution (a).

Department of Chemistry, Faculty of Science, Science University of Tokyo : Kagurazaka, Shinjuku-ku, Tokyo, Japan


Influence of Heat Aging Resistance on Chemical

Structure of Polyepichlorohydrin Rubber

by Kunio MORI and Yoshiro NAKAMURA

Four vulcanizing agents, Na2S • 9H2O-S, H2NCH2C112N1-12. H253-Mg0-S, Na2CS3-S and KCNS-CH3CON(CH3)2 were used

to improve the heat aging resistance of polyepichlorohydrin rubber. The heat aging resistance was observed by the . retention of the mechanical properties after air oven aging test. The heat aging resistance of the vulcanizates was compared with that of the vulcanizate containing the well-known vulcanizing agent H2NCH2CH2NH2-MgO. The former three vulcanizing agents, in the presence of proper sulfur contents, gave heat aging resistant vulcanizates containing di-, trisulfide or trithiocarbonate crosslinkages. The latter vulcanizing agent gave a rigid vulcanizate containing thio-cyanuric acid-type crosslinkages with low elongation and superior heat aging resistance.

Faculty of Engineering, Iwate University: Ueda, Morioka-shi, Japan



Mechanical Properties of NBR Vulcanizates Under Finite Defermation

by Yutaka OBATA*, Sueo KAWABATA** and Hiromichi KAWAI**

Generally, in order to determine the strain energy function W under finite deformation it is necessary to perform biaxial

experiment. So far not much work has been done in this connection. In the previous papers of the authors, the partial deriva-

tives of W with respect to strain invariants I and 12,

OW(11,12)1811 and OW(11,12)1012 for natural rubber (NR) and acrylonitrile-butadiene rubber (NBR) and the dependence of these functions on the degree of crosslinking and tem-

perature were reported. In the present paper, stress relaxation behavior under

orthogonal biaxial deformation is reported for three kinds of NBR samples with different acrylonitrile contents and the results obtained are as follows :

1) The relaxation function defined by Vt(Ai, 22) =MAD 22, t)/f(21, 22, 1= to) and (Pi(Ii, 12, t) =wg1,I2,01art)1(aw(I1,

12,t=tolor,)were plotted against Alfor strip biaxial deformation (22=1) data and it was found that ç, Co2 and Cbi increased with increasing Ai, while 02 was almost constant.

2) The material function 8 W(I1,./2,t=t0)1512 of NBR was very different from that for NR.

3) The depenence of Mooney Rivlin's constants C1 and C2 for NBR on the function owg1,I2,0181-, was very different from that of NR, and it is considered that W does not have a simple form such as W= 3) at equilibrium.

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

** Present address, Japan Synthetic Rubber Co. , Ltd. , Research Labolatory : Kawasaki, Japan


Softening of Polyurethane Elastomers*

by Yukio YAMAGUCHI**, Koretoshi UEMURA***, Tetsuo YOKOYAMA** and Takehide TANAKA**

A variety of polyurethanes containing polar groups, such as urethane, allophanate, urea, biuret and aromatic ring, in different concentrations have been synthesized by the pre-polymer method, and the relation between their chemical structure and softening has been investigated. In order to study the softening quantitatively, firstly the function

A.g(e)IB was derived, where B is the energy used for the first elongation process, A is the difference between B and the energy required for the fourth elongation process, and

g(e) is the corrective function for strain. The validity of this function was ascertained under various conditions. Next, softening of polyurethanes with different chemical structures was measured quantitatively. From the results it was concluded that polyurethanes containing urea and biuret groups caused the most softening, and that rigidity of main chain and steric hindrance arising from aromatic ring and side group effected the extent of softening. The origin of softening has been discussed.

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

Kyushu University: Hakozaki, Fukuoka, Japan *** Nissan Petrochemichal Industries , Ltd., Chiba Branch:

Ichihara, Chiba, Japan


Effects of Urethane Group on Properties of Polyurethanes*

by Yukio YAMAGUCHI, Tetsuo YOKOYAMA

and Takehide TANAKA**

The effects of urethane group on the properties of poly-urethanes have been studied. Polyurethanes with almost equal crosslinking density ([verV]) but with different ure-thane group concentration ([U/V]) were prepared by the

prepolymer method. The densities of the polyurethanes were not affected by [v0/ V]and [ V]. Although the swelling ratio (q) , the polymer-solvent interaction parameter

(X1) and the glass transition temperature (Tg) were not affected by [velV], q was found to decrease and X1 and Tg were found to increase with increasing [UIV]. On the other hand, the Young's modulus showed a maximum value at appropriate values of [ie/ 17] and [U/V]. These pheno-mena have been discussed in relation to the polymer struc-ture.

* Studies on Polyurethanes . XIV. 5* Department of Applied Chemistry, Faculty of Engineering,

Kyushu University : Hakozaki, Fukuoka, Japan

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


Structure and Mechanical Properties of Segmented Polyurethane Elastomer

by Ituro KIMURA, Hajime SUZUKI, Katsuo SAITO,

Kataro WATANABE, Hideaki ISHIHARA and Hiroshi ONO

A study on the mechanical properties and structure of segmented polyurethane polymerized from polytetramethylene

glycol, 4, 4'-diphenyl methane diisocyanate and diamines has been reported. From a study on the mechanism of

polymerization it was concluded that the co-polymer has blockiness in the sequence distribution of the segments., The deviation of the stress-strain relationship of the polymer from the predicted ideal rubber elasticity was related to the blockiness. Measurement of orientation showed the segment to be oriented transversely to the stretch direction . The deviation (including C2 term) was explained qualitatively by introducing a non-affine defomation mechanism. The structure of the aggregates of the hard segment was pro-

posed based on X-ray study, and was compared with the one proposed by Bonart.

Katata Research Institute, Toyobo Co. , Ltd. : Honkatata-cho, Otsu-shi, Shiga-ken, Japan

.... . ..,•.„,-----•,,,..,--„„„..--------.,.„.••„„.,,.,


Effect of r-Rays Irradiation on the Fine Structure and

Viscoelastic Properties of High Impact ABS Resin

by Satoshi NAGOU

The objective of this work is to investigate the effects of r-rays irradiation on the fine structure and viscoelastic

properties on high impact ABS resin. The results of the measurements of dynamic viscoelastic properties and mecha-nical properties, and the electron microscopic examination of ABS resin irradiated by r-rays to various total dose


were examined while paying special attention to crazing

(zone of molecular orientation) and comparing with those of unirradiated specimen.

When crosslinks were introduced by r-ray irradiation, a total dose higher than about 100 Mrad was not favorable as the specimen became brittle. However, when a total dose was lower than the value above mentioned, the oc-curence of crazing was prevented, and better mechanical

properties were also resulted.

Tokuyama Soda Co. , Ltd. : Mikage-cho, Tokuyama, Japan

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


Relaxation Phenomena in Dense Polystyrene and Polymethylmethacrylate

by Seiichi MANABE*, Nobuo KOBAYASHI**, Kiyohisa IMADA** and Motowo TAKAYANAGI**

The volume recovery and the dynamic viscoelastic pro-

perties of dense polymers of polystyrene(PS) and polymethyl-methacrylate(PMMA), which were prepared by glassifying the polymer melts under high pressures, have been investi-

gated. The volume recovery of the dense polymers occurred in two stages. The first one being the lower temperature

process taking place at about the temperature of 8a absorp-tion, which is associated with the twisting motion of the main chains around their axes and which is affected by con-formation, and the second one being the high temperature

process taking place near glass transition (Tg) , the major part of the density increase of the dense polymers results from the loss of the available free volume during the relaxation process of 8a absorption, which occurs at about

50°C for both PS and PMMA. These facts indicate that the formation of glass under

high pressure can not be characterized only by Tg as in the case of glassifying under normal pressure. The number of freezing parameters governing the glassy state change according to the temperature of the glass. The authors have tried to describe a glassy state in general on the assump-tion that the glass formation occurs through many stages associated with different freezing parameters characterizing the glassy state.

* Present address : Textile Research Laboratory, Asahi Chemical Ind., Ltd. : Takatsuki, Osaka, Japan

** Department of Applied Chemistry, Kyushu University: Fukuoka, Japan

.... ........ ,„, ... ..... „,,„„ ..... ...... „„...--- ......

Kogyo Kagaku Zasshi 73, 1566,-1571 (1970)

Mechanical Relaxations in Single Crystals of

Polyoxymethylene

by Kyosuke MIKI, Shigeki NAKAMURA

and Motozo KANEKO

The viscoelastic properties of single crystal mats of poly-

oxymethylene have been measured at temperatures between —150°C and 140°C . The measurements were made with a

forced-oscillation torsion pendulum at a constant frequency

of 0.5 Hz on the mats which had been annealed at various

temperatures near the melting point. The irradiation effect

of gamma rays on an annealed mat was also examined. In the original sample, five relaxation peaks, a, 1,31,

Ti and r2, were observed at approximately 130°C, 30°C, —10°C, — 75°C and —130°C, respectively. Upon annealing at progressively higher temperatures than 160°C, the a relaxation decreased in magnitude and the r, and r2 relaxa-tions shifted to higher temperatures. The 82 relaxation decreased in magnitude and shifted to a higher temperature upon annealing at 165°C. Upon annealing at 169°C, the 92 relaxation increased again in magnitude and exceeded that of the r1 relaxation. After annealing at a temperature above the melting point, the a, 9 and r relaxations were found to occur at the same temperatures as in the melt-crystallized sample. A strong peak was found at approximately —40°C for a sample which had been irradiated by gamma rays after annealing at 169°C.

Department of Polymer Science, Faculty of Science, Hokkaido University : Sapporo, Japan


Viscoelastic Properties and Crystal Transformation of Isotactic Polyoctadecene-1*

by Seiichi MANABE** and Motowo TAKAYANAGI***

Four viscoelastic absorptions were observed for isotactic

polyoctadecene-1 in the temperature range between —40°C and 30°C at 110 Hz. These absorptions were named ac'

ac" , aa' and a at from the high temperature side. The two absorptions, a,' and ac", were interpreted as due to mole-cular motions in the crystalline region, while the remaining absorptions, a a" and era', were considered to be due to molecular motions in the amorphous region and the amor-

phous-like region, respectively. The viscoelastic absorption cause by a local twisting motion of side chains was found at about —145°C.

The partially ordered form found in the quenched sample was transformed into the type I crystal reported by Turner-Jones at 40°C by the process of solid-liquid-solid transition, in which initially the side chains are transformed into the type I form, being followed by transformation of the main chains. Type I was gradually transformed into type Ii at about 63°C. This transformation occurred without obvious melting of the type I crystal. In this case, main chains and side chains were transformed into the type 11 from the type I crystal at the same time. The type ii crystal is thermodynamically the most stable among the two crystal forms; the partially ordered form is stable in the tempera-ture range between 20°C and 75°C.

* Viscoelastic Properties and Crystal Transformations of Poly-a-olefins with Unbranched Side Chains. I.

** Textile Research Laboratory, Asahi Chemical Ind., Ltd. : Takatsuki, Osaka, Japan

*** Department of Applied Chemistry, Kyushu University: Fukuooka, Japan



Structure and Viscoelastic Properties of Single Crystals

of Isotactic Polyoctadecene-1*

by Seiichi MANABE**, Shoji MINAMI***

and Motowo TAKAYANAGI***

Single crystals of isotactic polyoctadecene-1 (POD) were

prepared by two methods, the first employing isothermal crystallization from 0.01$ tetralin solution in the tempera-ture range from 0 to 15°C, and the second employing slow cooling of a solution of mixed solvents of methanol and xylene (volume ratio 1 : 4) from 55°C to 20°C with cooling rate of ca. 1°C/hr. The lattice constants of the crystal from the second method corresponded with those of the type n crystal reported by Turner-Jones.

The side chains in the crystals were oriented perpendicular to the basal plane of these crystals. The lamellae of these crystals were one or two molecular layers thick, i. e. 35-- 65 A. Although the electron diffraction patterns of the crystals from the first method agreed with those from the second method, new crystals with hexagonal structure with

a= 4.24 A were also found. The partially ordered form found by Turner-Jones is considered to apply to these new crystals. The viscoelastic properties of crystal mats prepared by the first method showed that the crystalline absorption

(a,") is large while those for aa' and aa" appeared as small shoulders. The absorption mechanisms for aa' and

aa" of the single crystals were considered to be caused by the loose molecules existing in the crystal sides. (For aa' and aa", refer to the previous paper in this series.)

The heat treatment of these mats had no effect on both the intensity and location of aci . This phenomenon is due to the fact that the side chains in the single crystals are already extended when crystallized and there is no possibility of thickening by heat treatment.

* Viscoelastc Properties and Crystal Transformations of Poly-a-olefins with Unbranched Side Chains. II.

** Textile Research Laboratory, Asahi Chemical Ind., Ltd. : Takatsuki, Osaka, Japan

*** Department of Applied Chemistry, Kyushu University: Fukuoka, Japan


Viscoelastic Properties and Crystal Transformation of Isotactic Polyhexadecene-1 and Polytetradecene-1*


The viscoelastic absorption an', a," , aa', aa", and were observed at 10°, —10°, —30°, —60°, —150°C for isotactic

polyhexadecene-1 (PHD). The apsorption mechanisms coin-cided with ones reported for polyoctadecene-1 (POD) in the

previous papers. The relaxation times of these absorptions in the case of PHD were found to be shorter than those for POD when a comparison was made under the same frequency and temperature conditions.

There were three types of crystal forms, one of which was the partially ordered form(pof). Pof transformed into the type I crystal reported by Turner-Jones through a solid-liquid-solid type transition. In this case, the side chains first assumed the order found in the type I form, followed by main chains. These results coincide with those of POD. The crystal transformation between the type

and type crystals was almost the same as that between PHD and POD.

The absorption a0", aa' , aa", and j9 observed at —14°, —36°, —48°, and —160°C (110 Hz) for polytetradecene-1

(PTD). In this case, ac' was absent. The decrease in the number of carbon atoms in side chains made the relaxation time of these absorptions shorter. The transformation of PTD from pof to the type I crystal occurred slowly in a temperature region below 20°C. The melting phenomena of

pof found in POD and PHD were not obvious for PTD. The melting points of the type I and type II crystals were found to be lowered with decreasing carbon numbers in the side chains from 70°C to 75°C for POD, from 60°C to 65°C for PHD, and from 52°C to 55°C for PTD.

Viscoelastic Properties and Crystal Transformations of Poly-e-olefins with Unbranched Side Chains. III.

" Textile Research Laboratory, Asahi Chemical Ind., Ltd. : Takatsuki, Osaka, Japan


.....


Viscoelastic Properties and Crystal Transformation of Isotactic Polydodecene-1, Polydecene-1,

Polyoctene-1 and Polypentene-1*

by Seiichi MANABE**, Hiroshi NAKAMURA***, Shinsaku UEMURA*** and Motowo TAKAYANAGI***

The temperature dependence of the viscoelasticity of iso-tactic polydodecene-1(PDD), polydecene-1(PD) and polyoc-tene-1 (PO) was similar in their shape of dispersion curve to those of polyoctadecene-1, polyhexadecene-1, and poly-tetradecene-1, that is, the aa' aa" and 8„ absorptions of these polymers were observed in this order from the high temperature side. The relaxation times of the corresponding absorptions became shorter with decreasing length of the side chains. The apparent activation energies of the absorp-tions aa' and aa" were estimated to be 55 and 50 kcal/mol, respectively, for PDD and 40 and 60 kcal/mol, respectively, for PD. The activation energy of aa' increased with increasing length of the side chains, while that of aa" decreased. The shape of dispersion curves of the polymers such as isotactic polypentene-1(PPe), whose side chains are com-posed of carbon atoms less than 6 and whose main chains are composed of helical conformations, was similar to that of isotactic polypropylene. These facts suggest that the local packing of molecules in the amorphous region is similar to that in the crystalline region.

More than two crystal forms were found for polydodecene-1, although the difference in their melting points could not be discriminated. Nematic or smectic crystals of PPe were obtained by quenching the melt of PPe in liquid nitrogen. The peak position in the X-ray diffraction patterns of these crystals nearly coincides with that for the melt. However, it was found that the main chain regularity of these crystals was higher than that of the melt.

Viscolaestic Properties and Crystal Transformations of Poly-e-olefins with Unbranched Side Chains. IV.

** Textile Research Laboratory, Asahi Chemical Ind. Ltd. : Takatsuki, Osaka, Japan




Effect of Chemical Structure on Viscoelasticity and

Crystal Transformation of Poly-a-olefins with

Unbranched Side Chains*


The viscoelasticity of poly-a-olefins with unbranched side chains was classified into two regions, one in which the number of side chain carbon atoms (N) is larger than 6 and the other where N is smaller than 6. The viscoelasticity when N>6 was mainly dependent on the motion and structue of side chains and when N was extremely large, it tended to that of polyethylene. The viscoelasticity when

N<6 was mainly dependent on the motion and structure of main chains and was similar to that of polypropylene (N=1).

The viscoelastic absorptions ac', ac", aa' (mc) , aa" (sc) and j9(sc) for poly-a-olefins with N>6, and ac, aa(mc),

8a(mc) and aa(sc) for poly-a-olefins with N<6 were measured from the high temperatured side. The suffixes a and c indicate that the absorption mechanisms are caused by the motion of the molecules in the crystalline region and the amorphous region, respectively, and mc and sc in parentheses indicate main chain and side chain, respec-tively. The mechanisms for aa"(sc) and 3a(sc) absorptions when N>6 correspond to the aa , and j9 absorptions, respec-tively, of polyethylene. The mechanisms for aa(mc) and

Ra(mc) absorption when N<6 correspond to the aa and R„ absorptions, respectively, of polypropylene.

From the linear dependence of the spacing in X-ray diffraction on N of the melt and the N dependence of viscoelasticity when the sample is in a glassy state, it was concluded that the conformation of molecules and the packing of molecular chains in the amorphous region are similar to those in the crystalline region, if a comparison is made concerning the local order.

The N dependence of melting points of the crystal forms indicates that the melting points of type if , type I and

partially ordered form coincide with the ones of n-paraffin with the numbers of side chain carbon atoms of (2N+2),

(2N) and (N+2), respectively.

Viscolaestic Properties and Crystal Transformations of Poly-e-olefins with Unbranched Side Chains. V.

*5 Textile Research Laboratory, Asahi Chemical Ind., Ltd. : Takatsuki, Osaka, Japan

*5* Department of Applied Chemistry : Fukuoka, Japan

Kogyo Kagaku Zasshi 73, 1602,-1610 (1970)

Viscoelastic Properties and Structure of Polymer

Blends and Block Copolymers

by Kenkichi MURAKAMI, Saburo TAMURA, Katsuo SHIINA and Taku UENO

This paper deals with the relation between the structure of monodisperse and polydisperse polymers, polymer blends, and block copolymers, and with their rheological properties.

It was found that the relaxation spectra of blended

polymers in which the molecular weights of both mono-disperse homopolymers are higher than their critical mole-cular weights Me show stepwise curves in the rubbery region of the spectrum, while those of blended polymers in which the molecular weight of one homopolymer is lower than Me give a typical box-type curve in the rubbery region of the spectrum.

Using the maximum relaxation time rm obtained by pro-cedure X, the value of rm ,bdrm,i, which is the ratio of

rm,bi of blended polymer to rm,i of homopolymer was

plotted against the ratio of weight average molecular weight of blended polymer to that of homopolymer. Murakami, et al. have theoretically obtained the relation between s" in,birm,i and /1/,,,bi/Mw,i or to give

rin,arm,i= (Mw,bi/Mw,i)", rm,blfrm,i (Mw,b1/Mw,i)2.4, and 'r (M n,b1/114-n,i) respectively.

These equations were compared with the experimental results and discussed. NMR was used for the identification of the structure of block-copolymers, and the relation bet-ween the semi-micro structure of butadiene block co-polymer and its viscoelastic properties was discussed.

Chemical Research Institute of Non-aqveous Solutions, Tohoku University : Sendai, Japan


Tensile Stress Relaxation Behavior of Mechanical

Mixture of Polypropylene and Polyethylene

by Tsuneo HORINO*, Etsuji IWAMI*,

Toshiichi SOEN** and Hiromichi KAWAI**

The tensile stress relaxation behavior of mechanically mixed polymer mixtures of polypropylene and polyethylene has been measured under a given small tensile strain at various temperatures ranging from room temperature to

120°C by using a chainomatic balance type autorecording relaxometer. The test specimens casted into films by using a hot press formed a crystalline texture of heterogeneous phases of polypropylene and polyethylene, which was proved by a polarization microscope investigation of these specimens.

The time temperature superposition procedure was carried out by shifting the relaxation modulus curves at room temperature to about 80°C along the long-time axis. The temperature dependence of the shift factors obtained by the superposition procedure was well approximated by the WLF type equation within the temperature range of glass transi-tion region and by the Arrhenius type equation within the transition region for crystalline parts of two component

polymers. The rheological properties of the mixtures depend on various factors, especially those of this mixed system are affected two factors, weight fraction and variation of cry-stallinity of two component polymers.

* Department of Textile Engineering, Art Industry and Textile College of Kyoto : Matsugasaki, Sakyo-ku, Kyoto, Japan

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

..... •••••••••••• ......... ••••• ................. • ................. •••• ......... •••


Tensile Stress Relaxation Behavior of Propylene-

Ethylene Copolymers

by Tsuneo HORINO*, Etsuji IWAMI*, Kaoru BAN*, Toshiichi SOEN** and Hiromichi KAWAI**

The temperature dependence of the tensile stress relaxa-tion behavior of two types of copolymerized systems, i.e. propylene-ethylene block copolymers and propylene-ethylene random copolymers, has been investigated using different


fractions of propylene component and compared with that of a mechanical mixture of polypropylene and polyethylene.

The test specimens casted into films by using a hot press showed a two-step melting behavior at particular tempera-tures, which corresponded to the melting points of two component polymer crystals.

The stress relaxation behavior of the block copolymer system resembled that of the mechanical mixtures except that a little lowering in the value of the relaxation modulus was observed. In contrast to this, the random copolymer system behaved like a crystalline polymer having low degree of crystallinity.

* Department of Texteile Engineering , Art Industry and Textile College of Kyoto : Matsugasaki, Sakyo-ku, Kyoto, Japan

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


Fine Texture in Bending Portions of U-Shaped

Specimens of Polyethylene

by Toshiaki SAKANO*, Seiji NAKAMURA*,

Shoji MANDAI*, Saburo ISHIKAWA* and Nobutami KASAI**

The fine texture in bending portions of U-shaped specimens of polyethylene has been investigated by means of X-ray diffraction. Two kinds of specimens, oriented and un- oriented, were used.

The outer surface of the bending portion of an oriented specimen gave a typical X-ray diagram with the (110),

(200), (020) and other reflections appearing as long arcs on the equator, i.e. on the radial direction of the specimen. In the case of an un-oriented specimen, however, the (200) reflections appeared as arcs on the equator, while the (020) reflections appeared as long arcs on the meridian, i.e. on the tangential direction of the bending. Best orientations were observed at an angle of about 50° from the bottom of U. In this case the a axis was found to orient ortho-

ganally to the tangential direction, the direction of the tension. On the inner surface of both the specimens, the (200)

reflections appeared as rather short arcs on the tangential direction.

It was concluded that in the initial stage of the bending, compression is dominant on the inner side of the U bend. The tension on the outer side is not so strong so as to give the typical uniaxial orientation.

* Textile Research Institute , Osaka Prefecture : Asahi-machi, Izumi-Otsu, Osaka, Japan

** Faculty of Engineering , Osaka University : Suita, Osaka, Japan


Mechanical Properties of Wood-Polymer

Composite Materials

by Mitsuhiro AKASHI, Tamio YASUKAWA and Kenkichi MURAKAMI

Various monomers were impregnated into wafers of birch and, thereafter, were polymerized by heating of gamma ray irradiation. The dynamic modulus of these samples was measured by using the free oscillation method. Generally,

the modulus of composite materials was found to increase

with polymer content, and the polymers with high glass

transition temperature and polar groups affected the modulus

remarkably than those which were rubbery at room tem-

perature. The temperature dependence of the modulus of

these composite materials was also related to the glass

transition temperature of the impregnated polymers.

The modulus of the wood powder-polymer systems were

much lower than those of the wood-polymer systems and

the effect of the glass transition temperature of impregnated

polymers in the former systems was less remarkable than

that in the latter ones.

Chemical Research Institute of Non-aqueous Solutions,

Tohoku University : Sendai, Jopan

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


Determination of Molecular Weight Distribution and Selection of Conditions for Rapid Fractionation by Column Elution Method for Polybutadienes*

by Toshio YOSHIMOTO and Seiya KANEKO**

In order to study the relation between molecular weight distributions of polybutadienes and their processabilities, conditions for rapid fractionation of the samples with very wide molecular weight distributions were established by the column elution method.

When a 2.5x30 cm column was used, about 0.3 g of a sample coated on celite (80-100 mesh) and placed in the upper part of the column was fractionated in about 6 hours at a constant temperature as low as 30°C by using toluene :

n-propanol.--- 75 : 25 and 55 : 45 as solvent and non-solvent, respectively. The non-solvent with its solvent proportion increasing logarithmically in a mixing chamber was sent to the top of the column at the rate of 50 m//hr. Under these conditions, even fractions having intrinsic viscosities [v] higher than 7 could be fractionated with good reproducibility.

In addition, strongly branched high molecular weight components could be qualitatively detected by a decrease in

[1i] with increasing molecular weight or by the phenomenon that [v] does not increase as much as the cumulative weight

percent increase.

Studies on Relations between Molecular Weight Distributions of Polybutadienes and Their Processabilities. I.

** Central Research Laboratory, Bridgestone Tire Co. Ltd. Kodaira-shi, Tokyo, Japan

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

Kogyo Kagaku Zasshi 73, 1634^-1638 (1970)

Relation between Molecular Weight Distribution

and Processability of Polybutadienes*

by Toshio YOSHIMOTO, Seiya KANEKO

and Tsunemasa NAKAJIMA**

The relation between molecular weight distributions of

polybutadienes and their processabilities has been studied, and it has been found that samples having a peak on the

low molecular weight side as well as a long tail on the

high molecular weight side showed good processability,

especially good roll processability.

For linear polybutadienes which were obtained by poly-

merization with a nickel based catalyst and had Mooney

A 88 Kogyo Kagaku Zasshi Vol. 73, No. 7 (1970)

viscosities between 40 and 50, their roll processability and cold flow property became good and tensile strength in the unvulcanized state became high as the content of low mole-cular weight components having [77] <1 increased. The improvement of one of these three properties tended to improve the other two properties at the same time. Thus, it is anticipated that processability of linear polybutadienes can be improved by allowing them to contain about 30% of the low molecular weight species with [77] <1 and at the same time to contain high molecular weight species in order to control the Mooney viscosity from 40 to 50.

* Studies on Relation between Molecular Weight Distributions of Polybutadienes and Their Processabilities. II.

5* Central Research Laboratory, Bridgestone Tire Co. Ltd. : Kodaira-shi, Tokyo, Japan

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


Relations between Relaxation Spectra, Molecular Weight Distribution and Processability of Polybutadienes*

by Toshio YOSHIMOTO, Seiya KANEKO

and Tsunemasa NAKAJIMA**

Relations between relaxation spectra, molecular weight distributions and processabilities of linear polybutadienes obtained by using a nickel based catalyst have been investi-

gated by determining relaxation spectra from relaxation modulus. It was revealed that the relaxation spectra of samples having Mooney viscosities between 40 and 50 ap-

proached to that of masticated natural rubber as the content of low molecular weight components having [7] <1 increased or as the processability, especially the roll processability, was improved. This result shows that the processability of a sample is decided by the degree of approach of its relaxation spectrum to that of masticated natural rubber.

The result enables us to interpret the fact that the undesirable roll processability of polybutadiene obtained by using a lithium based catalyst can be improved by blending it with masticated natural rubber. Therefore, relaxation spectra are useful for estimating the processabilities of samples such as polymer blends whose molecular weight distributions can not be measured easily.

* Studies on Relation between Molecular Weight Distributions of Polybutadienes and Their Processabilities. III.

.5 Central Research Laboratory, Bridgestone Tire Co. Ltd. : Kodaira-shi, Tokyo, Japan


Rheological Properties in Capillary Flow and Structure

of Molten Blends of Polyethylene with Ethylene Copolymers of Low Vinyl Acetate Content

by Toshikazu FUJIMURA and Kenji IWAKURA

In order to describe rheological properties of molten

polymer blends which contain a common monomer unit and to discuss the internal structure in the flowing state, the effects of comonomer content, blend composition, shear rate, temperature and nozzle dimension (LID) on the die swell and the pressure drop in capillary flow were studied

for molten blends of polyethylene with ethylene-vinyl acetate copolymers having low vinyl acetate contents.

1) The die swell showed complicated variation, including maxima and minima, with blending ratio and generally increased with increasing shear rate and decreased with increasing temperature at constant LID, but reverse behavior was observed near the maxima of die swell.

2) The elastic modulus evaluated from entrance pressure drop at different LID values showed complicated changes as in the case of die swell, but the modulus and the die swell did not show a perfect correspondence, relaxation phenomena must be considered to interpret this difference satisfactorily. 3) The variation of viscosity with composition deviated only a little from the additivity rule.

4) For the internal structure in the flowing state, a possibility of existence of intermediate structure due to partial compatibility between common units was suggested between phase seperation as island-in-sea model and homo-

geneous mixing. The change of these structures affects the interaction

between flow units and entanglement network distribution as in the cluster model and resulted in abnormal viscoelas-ticity of molten polymer blends.

Faculty of Engineering, Yamagata University : Jonan, Yonezawa-shi, Japan

ORIGINALS


Salt Effect in Vapor-Liquid Equilibrium of Methanol-Ethyl Acetate-Salt System

by Shuzo OHE, Kimihiko YOKOYAMA and Shoichi NAKAMURA

An azeotropic mixture can be separated into its pure components by azeotropic distillation with a volatile entrainer which will alter its vapor-liquid equilibrium. However , this can also be achieved by distillation with salt. The salt effect mainly, in alcohol-water systems has been exa-mined by various authors, but very little work has been done on other systems. In this study, the salt effect in vapor-liquid equilibrium of methanol-ethylacetate system at 1 atm has been examined with LiC1 and CaBr2. The dissolved

LiC1 concentrations were 1.97 mol in a liter of solvent and saturation at 25°C. In the case of CaBr2 the concentration was saturation at 25°C. LiC1 decreased the azeotropic com-

position from 72.5 molto 13.0 mol 0 but the azeotropic point was not eliminated. The x-y curves for each salt, and the boiling point data were obtained.

Research Institute, Ishikawajima-Harima Heavy Industries Co., Ltd. : Shin-Nakahara, Yokohama, Japan



Spectral Sensitization and Desensitization of Silver Halide Emulsion by Thiacyanines*

by Tadaaki TANI**

Based on the results obtained before, desensitizations by dyes have been classified into two types, the "desensitization by electron acceptor" and the "desensitization by halogen acceptor". Desensitization by desensitizing and infrared sensitizing dyes are attributed to the former type, which result from the promotion of the recombination process due to the capture of positive holes by these dyes. Desensitiza-tions by sensitizing dyes are attributed to the latter type, which result from the promotion of the recombination process due to the capture of free electrons by these dyes. In order to the clarify the above stated mechanisms, desensitizations by thiacyanines have been examined. Monomethine thia-cyanine did not show any desensitization. Trimethine thia-cyanine showed the desensitization by halogen acceptor. Pentamethine thiacyanine showed both the desensitization by halogen acceptor and that by electron acceptor. These results are consistent with the data about electronic structure of the dyes obtained in the earlier paper, and are therefore thought to support the above mentioned mechanisms for desensitization by dyes. The relation between desensitization and spectral sensitization by dyes has also been examined.

'1' Studies on Mechanism of Photographic Sensitivity . XXXVII. ** Research Laboratories, Ashigara, Fuji Photo Film Co. :

Minami-Ashigara, Kanagawa-ken, Japan


Water Vapor Adsorption by Fertilizer Salts

by Takafumi KANAZAWA, Masatoshi CHIKAZAWA and Mamoru KAIHO

Adsorption of water vapor on particles of some fertilizer salts has been measured, and their water vapor affinities have been compared and discussed. Five samples, urea compound fertilizer (UCF), high grade compound fertilizer

(HGCF), mixed compound fertilizer (MCF), lime nitrogen (LN) and urea (U) , were ground and used as the adsorbents.

The adsorption isotherms of water vapor on the samples were obtained at 0°C, — 8°C and —12°C. The BET plots of all the adsorbents except UCF showed straight lines in the range of relative pressures 0.1,-0.35. The water vapor

affinity, which is one of the solid surface properties, can be expressed by the ratio S (H20)/S (N2) , where S (H20) and

S (N2) are the surface areas obtained by using water vapor and N2, respectively. This ratio for all the samples was found to be lager than 1. This fact indicates that these salts have a considerable affinity for water vapor, the order of the magnitude being UCF>HGCF>MCF>LN>U. In the case of multilayer adsorption, the isosteric heat of adsorption determined for the three salts, UCF, HGCF and MCF, gave values which were smaller than the heat of liquefaction of water vapor.

The above results clearly prove that the process of water vapor adsorption on the fertilizer salts consists of not only a simple physical adsorption but also the diffusion of water molecules into salt particles and the dissolution of the salt at the surface by the water.

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


Design and Construction of a Table Mount Raman Spectrometer and Measurement of Laser-Exited Raman Spectra*

by Hiroshi TOMITA**, Yo-ichiro MASHIKO**

Teiichi SHIMOMURA***, Koji KIDA*** and Teruo KAJIURA****

The authors have designed and constructed a grating single monochromator with a plane grating of 1800 lines/mm blazed at 5000 A and a 18° off-axis paraboloidal mirror for recording Raman spectra photoelectrically.

The performance of the monochromator was tested by using a 4880 A Ar ion or a 6328 A He-Ne gas laser as the excitation source.

The relative optical speeds, dispersion and resolution by the spectrometer were satisfactory, and the spectra obtained were similar to those obtained with the usual double mono-chromators. This small table mount spectrometer was found suitable for use in analytical and physical chemistry.

* Technical Analyses by Optical Methods . XVII. ** The Government Chemical Industrial Research Institute , Tokyo:

Honmachi, Shibuya-ku, Tokyo, Japan *** Shimadzu Seisakusho, Ltd. : Nishinokyo, Kuwabara-cho,

Nakagyo-ku, Kyoto, Japan **** Japan Electron Optics Lab. Co. , Ltd. : Nakagami, Akishima,

Tokyo, Japan

Kogyo Kagaku Zasshi 73, 1664—.1667 (1970)

Analysis of Urethane Prepolymers by High Resolution NMR

by Kousuke KOBAYASHI, Kenji KURIHARA

and Kazutoyo HIROSE

Two well-defined peaks at 7.75 and 7.83 r, based on methyl

protons of 2,4-tolylene diisocyanate (TDI), have been observed in the measurement of polytetramethyleneglycol-TDI urethane prepolymers in 100 carbon tetrachloride solu-tions by a 100 MHz NMR spectrometer. The two peaks were assigned to the methyl protons of the para-reacted TDI and the di-reacted TDI with increasing field strength, respectively. The plot of the NCO/OH feed ratio vs. the mole-fraction of di-reacted TDI, which was measured from the area of the two peaks, agreed approximately with the theoretical curve which was calculated by assuming that the reactivity of the para-reacted TDI is less than that of free TDI. It is evident that the experimental curve is useful as a calibra-tion curve for estimating unknown NCO/OH feed ratios of the prepolymers.

The Dai-Nippon Institute of Chemical Research : Kamikizaki, Urawa-shi, Saitama-ken, Japan


Preparation of T-Crotonolacetone

by Kosuke YAMAMOTO

r-Crotonolactone was obtained in high yield by treating

8,7"-dichlorobutyric acid with calcium carbonate. When 8- hydroxy-r-chlorobutyric acid was used, a mixture of r-crotonolactone and 8-hydroxy-r-butyrolactone was obtained.


8-Hydroxy-8-chlorobutyronitrile was hydrolyzed in the presence of hydrochloric acid to give 8-hydroxy-r-chloro-

butyric acid which was pyrolysed into a mixture of 7.- crotonolactone and trans-r-chlorocrotonic acid.

When chlorovinyl acetic acid was treated with sodium hydroxide, a mixture of trans-r-hydroxy crotonic acid and

r,r'-oxydicrotonic acid was produced.

Ofuna Central Research Laboratory, Mitsui-Toatsu Chemicals, Inc. : Katsura-cho, Totsuka-ku, Yokohama, Japan


Study on Selectivity of Reaction of Isoprene Formation*

by Eiichiro NISHIKAWA, Toru UEKI and Yoshiro MORITA**

A study on the selectivity of the oxidative dehydrogena-tion reaction of isopentene, containing about 80% 3-methyl-1-butene, 10% 2-methyl-2-butene and 10% 2-methyl-l-butene, to isoprene has been carried out.

Three kinds of binary oxide catalysts of U-Sb, Sn-Sb and Bi-Mo, which were prepared by using the optimum

preparation condition for each catalyst, were used. It was observed that at the reaction temperature of 400°C

the selectivities to isoprene over these catalysts showed high values at low conversion levels, but decreased markedly with increasing isopentene conversion over the catalysts Sn-Sb and Bi-Mo. Over the U-Sb catalyst, however, high isoprene selectivity was maintained up to high conversion levels. The effects of oxygen partial pressure and reaction tem-

perature on the selectivity to isoprene formation at the same conversion were investigated using the U-Sb and Bi-Mo catalysts. Higher oxygen partial pressures lowered the selectivity over both these catalysts. The temperature dependence of selectivity over the Bi-Mo catalyst was rather small in the range from 375°C to 450°C, but the selectivity markedly decreased at reaction temperature higher than

400°C using the U-Sb catalyst.

* Catalytic Oxidative Dehydrogenation of Hydrocarbons . IV. 5* Department of Applied Chemistry, School of Science and

Engineering, Waseda University : Nishi-Okubo, Shinjuku-ku, Tokyo, Japan

........ ....••. ...... ........ ........ ........


Oxdation of Hydrocarbones with a Mixture of Nitric and Peracetic Acids in Acetic Acid

by Yoshiro OGATA, Atsushi KAWASAKI and Tetsuo NAKAMURA

Oxidation of hydrocarbons with a mixture of nitric and

peracetic acids in glacial acetic acid has been studied. Cyclohexane, ethylbenzene, and diphenylmethane gave the corresponding alcohols, acetates and ketones. The oxidation of ethylbenzene gave the total yield of oxidized products

(alcohol+ acetate + ketone) below 10%, the major product being acetophenone. But the total yield rose to ca. 40% by the addition of aluminum nitrate to the reaction mixture. In this case the major products were a-phenylethyl alcohol and a-phenylethyl acetate (each ca. 15%), since oxidation

of the alcohol and acetate to the ketone was suppressed to increase yields of the alcohol and acetate. The total yield

of the corresponding alcohol, acetate and ketone from diphenylmethane increased from 20% to 60% on addition of

aluminum nitrate. The oxidation was less satisfactory with cyclohexane, where the yields of alcohol and acetate were low (below 10%) and other products of higher boiling point were formed even with the addition of aluminum nitrate.

Cumene gave acetophenone (about 10%) as the sole product, neither cumyl alcohol nor the acetate being formed regardless of the presence or absence of aluminum nitrate.

Department of Applied Chemistry, Faculty of Engineering, Nagoya University : Chikusa-ku, Nagoya, Japan


Reaction of 1,2-Epoxyoctane with Benzene in Presence of Excess AlC13*

by Shunsuke HATA, Ken ONO, Haruo MATSUDA and Sumio MATSUDA**

The reaction between 1,2-epoxyoctane and benzene in the

presence of an excess amount of AlC13 yielded considerable amounts of abnormal products, 1-, 3-, 4-, 5-, 6-, and 7-

pheny1-1-octanol, in addition to the ordinary products 2- phenyl-l-octanol, as the main product, and 1-phenyloctane,

2-chloro-1-octanol and 1-chloro-2-octanol, as by-products. No other products from the isomerization of phenyloctanols were isolated. On treating chloro-octanol with an excess amount of A1C13 in benzene, all the isomeric phenyloctanols were obtained. From the above facts, it seems most reaso-nable to conclude that the isomerization of the carbonium

ion, CH3(CH2)5CHCH20A1C12, from chloro-octanol and A1C13 occurs through a one step hydride shift in the acyclic compound.

* Reactions and Utilizations of Higher Alkene Oxides. VII. *5 Faculty of Engineering , Osaka University : Yamadakami, Suita,

Japan

•. ..... ...... ..... ............ ....... .•••


Reaction Rate of 2,4-Tolylenediisocyanate and Methyl Alcohol*

by Senji ITO and Yotaro TSUTSUMI**

The kinetics of the spontaneous and triethylamine (TEA)- catalyzed reactions of 2,4-tolylenediisocyanate (2,4-TDI) with methyl alcohol(Me0H) have been studied. In the

presence of TEA catalyst the second-order rate constants in the initial step were proportional to the concentration of

TEA. On the other hand, in the spontaneous reactions the second-order initial rate constants were found to be in-dependent of the concentration of isocyanate, but greatly dependent on the concentration of OH. The equation for the second-order initial rate constants can be written as

k = 0.00099 (OH)/ (0.348 + (OH) ) + 0.0013 (OH) The spontaneous reaction was considered to be a competitive reaction of the bimolecular and trimolecular mechanism , which took place at low and high alcohol concentrations, respectively, giving rise to complex formation.

The rate constants of several other alcohols were also


investigated without a catalyst. It was found that the apparent second-order rate constants were in the decreasing order of methyl, ethyl isopropyl and tert-butyl alcohol.

'1' Reaction Rate Study of 2,4-Tolylenediisocyanate with Alcohols. I.

** The Composite Research & Development Center of Toyo Seikan and Toyo Kohan Companies : Okazawa-cho, Hodogaya-ku, Yokohama,

Japan


Analytical Study of Aggregation by Maximum

Slope Method

by Teruko SANUKI and Mitsuhiko HIDA

The maximum slope method and the minimum deviation method, presented previously by one of the authors, have

proved advantageous to determine the aggregation constant and the degree of aggregation of organic compounds from electronic spectra measurements.

In this paper, errors included in the aggregation para-meters obtained by the maximum slope method will be discussed. In the case of single equilibrium systems, the mean deviation of the observed absorptivity from the calcu-one was found to increase steeply with error of aggregation

parameters. The maximum slope method may be used to obtain accurate aggregation parameters. The determination of aggregation parameters of a complex equilibrium is, however, rather difficult, since the increament in mean deviation with error of aggregation parameters is not so large. Aminoanthraquinonesulfonic acids aggregate into dimers

in an aqueous solvent, and their absorption spectra in the visible region shift bathochromically with dimer formation. The aggregation constants were determined by the maximum slope method and possible structures of the dimer were discussed.

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


Azo Dyes from Aminoimidazoles*

by Kiroku KOMATSU**, Michinobu KAIMORI***, Kenzo KONISHI** and Nobuhiko KUROKI**

2,4(or 2,5)-Dimethyl-5(or 4)-aminoimidazole was found to diazotize with sodium nitrite and hydrochloric acid and couple with phenoles.

Mono azo dyes containing the dimethylimidazole ring were

prepared by coupling with 2-naphthol, 2-hydroxy-3-naphthoic acid, 2-hydroxy-3-naphthanilide, 1-phenyl-3-methyl-5-pyra-zolone and resorcinol.

The azo dyes have not yet been prepared from amino-imidazoles as diazo components, but it was only reported long time back that 5-amino-4-methylimidazole was diazo-tized and coupled with 2-naphthol.

Since imidazoles can form complexes with transition metals and have the basic nitrogen, these dyes were applied on metalsalt modified polypropylene fibers and acrylic fibers

(Cashimilon F). The dyeing ability of these dyes and the shade and fastness of the dyeings were discussed. The dye from 1-phenyl-3-methyl-5-pyrazolone gives a deep shade and excellent fast dyeing on nickelsalt modified polypropylene fiber and on Cashimilon F.

Azo dyes using 2-p-aminophenylimidazole as the diazo

component were prepared. Since these dyes have an imida-

zole ring not directly attached to the azo linkage, the dyes

gave poor results on metalsalt modified polypropylene fibers.

Studies on Azo Dyes Containing Imidazole Ring. IV. ** Department of Applied Chemistry, Faculty of Engineering,

University of Osaka Prefecture : Mozu, Sakai, Osaka, Japan *** Kanegabuchi Spinning Co. , Ltd. : Ogaki, Gifu, Japan

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


Ligand-Ligand Coupling Reactions of r-Allylic Palladium

Complexes in Presence of Carbon Monoxide

by Yasutaka TAKAHASHI, Takeo INAGAKI,

Hiroshi MORI, Mitsuhiko SAKAKIBARA,

Shizuyoshi SAKAI and Yoshio ISHII

acetylacetonato- and acetoxypalladium complexes, were found to decompose under carbon monoxide to give the corresponding ligand-ligand coupling products, allylic acetylacetones and acetate esters, and N-allyl-substituted anilines, respectively. Bis(substituted n-cinnamylpalladium chloride) complexes reacted in the CO-CH3OH-KOH system to give the corresponding cinnamyl methyl ethers and dicinnamyls, while the reaction products were propenyl-benzenes and/or propylbenzenes if a similar reaction was

performed without carbon monoxide. These coupling reac-tions proceeded more smoothly in polar solvents than in non-polar ones. The asymmetrically substituted 7r-allylic complexes generally gave the two expected isomers, but only one of the isomers was obtaind from 4-butenylallyl complex by probable anchimeric assistance of double bond included in its substituent.

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


Sensitized Photodegradation of Cellulose by Anthraquinone and Its Derivatives. II.*

by Chiugo KUJIRAI, Kyoji TSUBAKIYAMA, Naonori HONDA and Ken-ichiro TODA**

Firstly, for comparison of the sensitization activities of the 7r—n and n—n-* transitions of anthraquinone(AQ) and its derivatives against those of cellulose photodegradation, their relative quantum efficiencies (r) were first determined by an indirect calculation method with AQ-8-SO3Na, and the value obtained for r(z—n*) : r(n—n*) was 1 : 100. Next, the absolute quantum efficiencies (P) of the n—n* and n—n* transitions for the above sensitizer were measured in order to compare the quantum efficiencies of the direct and sensitized photodegradations. As a result, different effects were observed according to the transition, that is, the n— n-* transition rather inhibited the photodegradation while the n—n-* transition accelerated it compared with direct photodegradation.

Os were also examined with AQ substituted by various

groups in the j3-position. In the case of sensitized photo-degradation by n 7r* transition, its activity was not so effected by the introduction of an electron attracting group compared with AQ itself, but on substituting with an electron donating group the efficiencies were markedly

A 92 Kogyo Kagaku Zasshi Vol. 73, No. 7 (1970)

decreased. On the other hand, degradation by the 7r -z* transition was almost independent of the type of the sub-stituted group.

The sensitized photodegradation of cellulose by AQ-8- SO3Na exhibited strong after effect in oxygen atmosphere. Under the experimental condition, this after effect continued to be observed for at least four days. The existence of this effect suggests that the sensitized photodegradation

proceeds by a chain reaction in the presence of oxygen. In vacuo, this phenomenon was not observed.

* Studies on the Photodegradation of Cellulose. IX. *5 Textile Research Institute , Faculty of Engineering,

Fukui University : Bunkyo, Fukui, Japan


Continuous Solution Polymerization of Methyl Methacrylate

by Masaomi TAKAO, Soo-il LEE and Tatsuya IMOTO

The MMA-AIBN-toluene polymerization in batch and flow reactors was analyzed based on a dimensionless polymeriza-tion model developed by the authors. The model parameters were estimated experimentally from measured conversion curves and average molecular weight of the polymer pro-ducts. In addition, the termination kinetics by recombina-tion are discussed as an important factor for explaining the molecular weight distribution of the product in the flow reactor as measured by both gel permeation chromatography and Spencer fractionation.

Faculty of Education, Kagawa University : Saiwai-cho, Takamatsu, Japan

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Copolymerization of Diallylidenepentaerythritol with Maleic Anhydride*

by Tatsuro OUCHI and Masayoshi OIWA**

Diallylidenepentaerythritol(DAPE) was copolymerized with maleic anhydride(Manh) under various conditions, using benzoyl peroxide as an initiator. Although the ratio of the allylidene group to Manh incorporated into the polymer was almost equal, it varied slightly with the monomer composition and concentration. The formation of a molecular complex during the copolymerization was assumed from the fact that the rate of copolymerization had a maximum at the monomer feed ratio ([DAPE]/[Manh]) of 0.5, and from UV-spectroscopic analyses of the monomer mixture.

It was kinetically estimated that the copolymerization might proceed via the pseudo-terpolymerization of the allyli-dene group, Manh and the charge transfer complex formed

therefrom. The following functional group reactivity ratios were obtained at 60°C.

DAPE (MO - Manh (M2) ricK = 0.76 r2,K= 0.055

r1=0.08 r2=0.03 where K is the equilibrium constant of the complex forma-tion. * Studies of Polymerization of Diallylidenepentaerythritol . VI. ** Department of Applied Chemistry, Faculty of Engineering,

Kansai University: Senriyama, Suita-shi, Osaka, Japan

Kogyo Kagaku Zasshi 73, 1717---1719 (1970)

Copolymerization of 2-Vinyl-1,3-dioxolane with Maleic Anhydride*

by Tatsuro OUCHI and Masayoshi OIWA**

The copolymerization of 2-vinyl-1,-3-dioxolane(VDOL) with maleic anhydride(Manh) was carried out, using benzoyl

peroxide as an initiator. The polymer composition varied slightly with the monomer composition and with the monomer concentration. From the result that the rate of copolymerization had a

maximum at the monomer feed ratio ([VDOL]/[Manh]) of 1.00, and from UV-spectroscopic analyses of the monomer mixture, it was concluded that the copolymerization might

proceed via the pseudo-terpolymerization of allylidene group, Manh and the charge transfer complex formed therefrom.

The following functional group reactivity ratios were ob-tained at 60°C on VDOL (MI) -Manh(M2) system.

ricK= 0.440.053 r1=0.12r2eK= r2=0.17

where K is the equilibrium constant of the complex forma-tion.

* Studies on Polymerization of Diallylidenepentaerythritol . VII. ** Department of Applied Chemistry, Faculty of Engineering,

Kansai University : Senriyama, Suita-shi, Osaka, Japan


Syntheses of Branched Polyamideamine Copolymers and Graft Polyesteramides*

by Shitomi KATAYAMA, Hideichi HORIKAWA and Yukio OBUCHI**

N-(6-Aminohexy1)8-alanine( I ), which was prepared by the reaction of8-propiolactone(PL) with hexamethylenedia- mine, yielded branched polyamideamine copolymers( Ii ) upon copolymerization with e-amino-n-caproic acid. PL reacted

with ( II ) without solvent or in acetnitrile to give graft

polyesteramides(i11). The degree of branching of the homo-polymer of ( I ) was 950. ( II) with f2>0.3 (f2 is the initial mole fraction of ( I ) in the feed) were soluble in water and alcohol, showed amorphous X-ray diffraction

patterns, and the solutions gave red color with phenol-phthalein. Characteristic properties were studied . for the

polymers(ii) and (HI) with f1<0.2, which were insoluble in water and or alcohol. ( iI ) had intrinsic viscosity of

0.51-.'0.95, m.p. 176-224°C and density of 1.17±1.01, and showed the same crystalline diagram as that for the a-structure of 6-nylon, with the crystallinity decreasing with increasing f2. (BI) prepared without solvent had inherent viscosity of m.p. 168-•,227°C, density 1.23±0.02,

graft chain length 11.6,...,101.5 (in monomer units), and graft ratio 137-254 (mol/100 mol of monomer units of the stem

polymer). (III) prepared in acetonitrile had inherent vis-cosity of 0.40,-0.98, m.p. 178,-224°C, density 1.16+0.01,

graft chain length 3.77-7.28, and graft ratio 20.5-67.3. An equation relating the melting point ( T°K) of copolymers with the compositions (N mole fraction) was proposed as

follows; 11T-11(gT0),-----R1(h4H) ln N, where g is related with the graft chain length and h with the sequence length


of copolymers. This equation was applicable not only to random linear copolymers, but also to branched, graft and block copolymers.

* Studies on Polycondensation and Polyaddition Copolymers . I. ** Department of Fuel Chemistry, Faculty of Mining Science and

Technology, University of Akita : Tegata, Akita, Japan


Influence of Solvents on Epoxidation of Olefins with Peracid Type Resins*

by Toru TAKAGI, Jun KITAGAWA and Masahiro AOYAMA**

The epoxidation of olefins has been investigated kinetically. Epoxidation of cyclohexene with the peracid type resins and

perbenzoic acid was carried out in various solvents at 10—, 30°C. With increasing solvent polarity, the rate of epoxida-

tion showed a decrease when perbenzoic acid was used, while the rate increased when the peracid type resins were used. The results were discussed in terms of several factors. The carbonyl and hydroxyl streching absorptions of the peracid type resins in various solvents appeared in the narrow spectral regions, which suggests to the protection of peracid groups from solvation with the resin matrix. Increasing of the distribution coefficients and the swelling with polar solvents will probably accelerate the reaction.

In the epoxidation of a-olefins with the peracid type resins, tert-butyl alcohol has been found to be useful as a solvent because of excellent stability. When C5---,C 16 -- olefins were epoxidized at 20-30°C, C7-.-C9 olefins were oxidized with the maximum rate. The rapid conversion of the higher olefins above 806/9 to the corresponding epoxides was attained by oxidation at high temperature (50-40°C) with excess reagent.

* Peracid Type Polymers. VI. ** Faculty of Engineering , Nagoya University: Nagoya, Japan

NOTE


The Reactions of sec-Butylbenzenes Induced

by Aluminum Chloride*

by Yoshihide OKAMI, Sawako HAMANAKA,

Kazuyoshi ITOH and Masaya OGAWA**

In the reactions of sec-butylated benzenes induced by

aluminum chloride, the relation between transalkylation and

isomerization was investigated. Without any special caution

for moisture, the isomerization where the sec-butyl group

isomerized to the isobutyl group, proceeded slowly after

obtaining the transalkylated products in equilibrium.

Thus, the isomerized products probably do not result

directly from transalkylation. Under the anhydrous condi-

tions, any products of both reactions were not obtained.

* The Reaction of Alkylbenzenes . VII. ** Department of Applied Chemistry , Faculty of Engineering,

Kansai University : Senriyama, Suita-shi, Osaka, Japan

LETTER TO THE EDITOR


Recovering SO2 from Exhausted Gases Containing 502

by Toyoshi ASANO

Exhausted gases from petrochemical industry plants or

power plants contain SO2 which at present is causing air

pollution greatly. The gases are contacted with the stream of manganese

or slurry countercurrently at elevated temperature. React-

ing with the slurry components, the gaseous SO2 is converted

to aqueous H2SO4 with the concentration of lead chamber

process grade.

Tekkosha Co., Ltd. : 3-Chome, Kyobashi, Chuo-ku, Tokyo, Japan

kogyo kagaku zasshi - jst

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