The hydrogen bonding in the nitrogen-containing linkages of allophanate and biuret compounds has been studied by using IR and NMR spectroscopy.
From the IR spectra in a dilute carbon tetrachloride solution, the NH proton of ethyl α, γ -diphenylallophanate (1) was shown to be, cempletely hydrogen-bonded, whereas there are both free and bonded NH hydrogens in the case of 1, 3, 5-triphenylbiuret (2). From the above results and the NMR spectra of the NH proton of these compounds in the mixed solvent system, carbon tetrachloride-dimethyl sulfoxide, it was shown that (1) has one conformation shown in structure (1 a), while (2) posseses two conformations (2 a) and (2 b), where the interconversion between two conformations occurs. lt follows that the NH proton of (2)resonates at a higher field than that of (1).
In the cases of unsymmetrical biurets such as 1-(o-chlorophenyl)-3, 5-(8) and 1-(o-bromophenyl)-3, 5-diphenylbiurets (9), the results of NMR spectra in the mixed solvent system (deuteriochloroform-dimethylsulfoxide) indicated that the conformation (8 a) (or (9 a)) is
predominant in deuteriochloroform, while the conformation (8 b) (or (9 b)) is preferred in the polar solvent like dimethyl sulfoxide.

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Adsorption isotherms of carbon dioxide on four kinds of activated carbons were measured at temperatures of 25C, 50C and 75C, and at pressures up to 170 atm (Figs.1-4). For almost all cases, adsorption isotherms with maxima were obtained, but depending on the differences of the nature of the adsorbent carbons, the shapes of the isotherms and the fugacities (fmax, Table 2) which gave the maximum adsorption differed widely.
It was found that the smaller is the pore size of the adsorbent the lower is the fugacity fmax (Table 1, 2) by investigating the correlations between the fmax values and the pore size distribution curves (Fig.5) (or mean pore sizes (Table 1)) calculated from low temperature nitrogen adsorption date.
Taking the pore size distribution into consideration, a prediction of the adsorption isothetm was carried out and it was compared with the experimental data. lt was demonstrated that the precision of this method is superior to that of the previously proposed prediction method in which only the mean pote size had been taken into consideration (Figs.9-14, Table 3).

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Dehydrogenation to toluene and dehydro-demethylation to benzene of methyicyclohexane over silica-supported nickel cata1yst have been studied by using a conventional pulse-reaction apparatus at temperatures of 230 to 340C. Effects of the catalyst sulfuration on selectivity of the reactions were also investigated.
The catalyst activity was almost constant during the repeated sample injections. The conversion data were approximately expressed by Eq. (4) representing the one-half order kinetics. The dehydro-demethylation and hydrocracking reactions were retarded with an increase in C4H4S dosage, whereas the dehydrogenation to toluene remained unchanged at the initiql stage of the catalyst sulfuration. The catalyst was completely poisoned by the addition of 6x10-5 mol/g-cat C4H4S When the completely poisoned catalyst was partially reduced in a stteam of hydrogen at temperature near 450C, it showed an excellent selectivity for a dehydrogenation to toluene. The partially sulfurated nickel was similar in catalytic selectivity to platinum catalyst, as Kwan et al. have already pointed out with regard to the various hydrogenation reactions.

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Tbe rgactiops of curpene and isopropylcyclohexane (IPCH) on sulfided molybdena-alumina catalyst have been studid under 10-200 atm of hydrogen pressure and at the temperatute ranging from 350 to 450C.
Cumene was gydrocracked to be propane and bezene, while IPCH was converted to C9-naphthene isomers, cumene and C9-aromatic isomers.
The rate of hydrodealkylation of cumene (vd), and the rate of conversion of IPCH(vt) were given by following relations:
vd=k[KcPc/(1+KBPB+KcPc+K1P1/KH√ PH)][KH√ PH/(1+KH√ PH)]
v1=k'[K1'P1(KH√ PH)/(1+ K1'P1/KH√ PH)][1/(1+KH√ PH)]
where k and k' are the rate constants, Pi, PB, Pc and PH are. the partial pressure of IPCH, benzene, cumene and H2, respectively.
The values of Kr, KB, Kc and KH at 400C were given by 1.58, O.82, 1.92 atm-1, and 0.10atm-0.5 for vd, while K1' was given by O.07 atm-1 for vt. The remarkable differece in Ki and Ki' suggests that the catalyst has different active sites for these two reqctions.

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The vapor phase oxidation of C3H6 or i-C4Hs over binary catalysts of MoO3 and other oxides (MOm/2) have been investigated in relation to the effect of the added oxides on the activity. The reaction was carried out with 17% C3H6 or 15% i-C4Hs in air. The binary catalysts were investigated mostly in the composition of M/MO=O.2 (atomic ratio), with several exceptional cases of M/Mo=1. The orders of catalystic activity of C3H6 and i-C4H8 oxidation were the same. The activity order was as fo11ews:
(Mo-Ti)> Mo-Sn> Mo-Cr> Mo-V> Mo-Mn> Me-P> Mo-Ce=Mo--Fe at Mo-Co=Me--Sb=MeO3,
while the orders of the yields of the unsaturated aldehydes were
Mo-Sn> Mo--Cr> Mo-Mn> Mo-V> (Mo-Ti)> Mo-Fe> Mo-Ce: Me-Ce=Mo-P=Mo-Sb> MoO3
(the yield of acrelein at 450C)
Mo-Cr> Mo-V> Mo-Mn> Mo-Sn> (Me-Ti) > Mo-Sb> Me-Fe> Me-Co> Mo-Ce> Mo-P> MoO3
(the yield of methacrolein at 420C)
On the assumption that the reactivity of surface oxygen reflected in the extent of deep oxidation, the amount of CO+CO2, formed at the initial stage of the reduction of catalyst with CsH6 (in N2), was adopted as the reactivity index. lt is found that the oxidation activity was dependent on the reactivity of surface oxygen. Further, when the difference of ionic radii between Mm+ and Mo6+ was large, the oxidation activity was high (Fig.9 and 10)
Ori the basis of these results, it is suggested that the strain introduced by the added oxide into MoOs lattice increases the catalytic activity.

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The states of hydrogen sorbed by palladium black and supported palladium were studied by measiuring the heat of aasorption using a twin calorimeter.
The inital heat of adsorption was 18 kcal/mol for palladium black and 35 kcal/mol for supported paHadium (O.43 wt % Pd/Silica-Alumina) and the heat of adsorption decreased with increasing the amount of hydrogen adsorbed (Fig.5).
The three states of hydrogen, strongly adsorbed hydrogen (H, ), dissolved hydrogen (Hd), and weakly adsorbed hydrogen (H.), were identified by comparing the values of exothermic heat with the adsorption isotherm.
The amount of H, dqcreases with the increasing Pd-eontent in the case of supported palladium. lt was observed the H, hardly desorbed, while Hd and H. easily desorb on evacuation (Fig.7).
The result with the CO-treated catalyst shows that chemisorbed carbon monoxide poisons exclusively the sites of H, (Fig.9).

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Thermal decomposition reaction of NH4VO3 was carried out by means of gas-flow DTA apparatus in which air flowed through the sample bed, by the flow rate of 700, 500, 100, O ml/min. Nitrogen gas and wet air with the flow rate of 100 ml/min, and vacuum atmosphere were also employed. From the analyses of the X-ray diffraction patterns of decomposition products ebtained at various temperatures, two kinds of new intermediates (designated as M4and M5)were discovered(Fig., 6)in addition to three intermediates I, II and III(designated as M1, M2 and M3) which have been already reported by Kato et al. (Ref.8). The color of M4 and M5 was blue, while that of M1, M2 and M3 was brown. IR spectra of M4 and M5 had an absorption band of NH4+ near 1400 cm-1 and resembled those of VgO13 between 800 and 1000 cm-1 (Fig.11). ln the courses of decomposition, M1 and M2 were observed at low partial pressures of NH3 and H2O (vacuum system and air flow rate of 700 ml/min (Fig.2)), M1, M2, M3 and M4 at medium partial pressures (air flow rate: 500 and 100 ml/min (Fig.3 and 4)), M2, M3, M4 and M5 at high partial pressures (static air and closed system (Fig.5, 7 and 8)) and M 2, M 3 and M 4 at high partial pressure of H20 (wet air (Fig.10)).
Ml, M2 and M3 were formed directly from NH4 3, while M4 and M5 were formed through M2 or M3. The partial pressure of 02 had no influence on the kind of the intermediates formed but had influence on that of the final products. The lower oxides of vanadium such as V307, V6O13 and V2O4 were formed at low partial pressure of 02 (Fig.5, 7 8 and 9).

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The preparation of zine oxide thin film by reactive sputtering was attempted. A convenew tional diode-type RF sputtering apparatus was employed.
Sputtering conditions were as fellows: Target; Zn plate (150 mmψ), Pressure of mixed gas; 3X10-3 mmHg, Volume ratie of mixed gas; Ar: O2=7: 1, Substrate: Slide glass or NESA glass.
Zinc oxide film thus obtained was very adhesive to substrate and had uniform thickness over a wide range of surface area. Film thickness increased linearly with sputtering time, indicating that sputtering proceeded without being interfered with the insulating layer formed on the Zn target during sputtering. The deposition rate at the plate voltage of 2, 6kV was 30A-40 A/min, which was increased linearly with increasing plate voltage.

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It is well known that the ferromagnetic fine powder of CrO2 can be obtained by the hydrothermal decomposition of CrO3 or the dehydration and oxydation of Cr(OH)3 under high oxYgen pressure. However, the dissociation processes of CrO3 and Cr(OH)3under high oxygen pressure at elevated temperature have not been fully investigated. Moreover, the peak of DTA which shows the formation of CrO2 phase has not been fined yet under atmospheric pressure. The DTA. measurement under high oxygen pressure seems to be available to elucidate the transformation process to CrO2, and the transformation temperature region.
The mechanism of the formation of CrO2 was studied by the apparatus which is specially designed for measurements, under high oxygen pressure. As a starting material, 500 mg of CrO3 was used. Although three, peaks were observed under high oxygen pressure, no peak that corresponds to the formation of CrO2 was observed. lt was considered that the poor thermal cohtact between l0 1idied Cr20sd thermocouple made difficult to detect the CrO2peak. To improve the thermal contact, fine powder of Cr20s was used as a starting material, so that 3 faint endothermic peak was observed at about 420C. It was conmed by X-ray analysis that this peak correspopds to the formation of CrO2,
When Cr(OH)3 was used as a starting material, the oxidatien, the reduction and the crystal transformation of the specimen oecutred during the dissociation process, so that the DTA curve Showed More corn, plicated behavior than of CrO3.

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Graphite single crystals were grown by the solidification of the melt under high temperature and high pressure of 2 kb, using carbon black rod as a starting material and a heater. The carbon black contains negligible amounts of iron, calcium and titanium as impurities.
A piston-cylinder type high pressure apparatus was used for all the experiments and temperature was presented by the terms of electric power-input(II) because of the difficulty of temperature correction under high pressure.
Graptsingle crystals were grown on the surface of the heater above 1020 W at 2 kb, with maximum dimension of about 12.0 X 10.0 mm2 and thickness of fraction of a millimeter. lt seems fairly obvious that the elements contained in pyrophyllite played important roles for the growth of graphite single crystal.
Graphite single crystals with metallic luster and well-defined edges were grown in the inner part of the heater above 1400 W at 2 kb, maximum dimension being about 1.20 X O.85 mm2.
Twin boundary cracks were observed on graphite single crystals grown. The measured angles between two adjacent planes were 16.40 and 11.10.
In some experiments, spheres of graphite crystals with up to about 1.35 mm in diameter were observed near the central part of the heater. Their basal planes of small each graphite single crystals were generally orientated parallel to the circumference of crystal sphere,
From X-ray diffraction patterns, it was evident that grown graphite cystals had lattice spacings close to the values of natural graphite reported in literatures.

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The defibrillation of chrysotile asbestos with anionic surface active agent was invesktigated. Chrysotile asbestos from Barberton district and anionic surfactant Aerosol-OT were used for this study. From the observation of defibrillation behavior with optical microscope and the result of DTA measurment, it was revealed that the defibrillation occurs at the Aerosol-OT equilibrium concentration between 400 mg/l and 1100 mg/l, at which the second layer adsorption of Aerosol-OT takes place.
As the molecules of Aerosol-OT of second layer are adsorbed with their polar heads directed towards the solution on the non-polar heads of the first layer molecules of Aerosol-OT, the defibrillation of chrysotile with Aerosol-OT is induced partly by the hydrophillic property of these polar heads, and partly by the repulsion property between fibriHs covered with two layers of Aerosol-OT.
It was concluded from the results of adsorption isotherm, and re1ationships among the equilibrium concentration, specific surface area and sedimentation volume, that two different defibrillation mechanisms exist at different equilibrium concentrations. The one observed mainly at the concentration between 400 mg/l and 800 mg/l and is due to the dispersing effect of Aerosol-OT, the others observed at the concentration between 800 mg/l and 1100 mg/l, which accompanies the destruction of bonding between individual fibrills. The former shows no change in specific surface area, the latter has a distinct increase of specific surface area and amount of adsorptien of Aerosol-OT.
The specific surface area of chrysotile asbestos difibrillated with Aerosol-OT reaches to 63-65 m2/g, which are almost similar with that of meehanically defibrillated fiber.

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The complexes formed between copper(II) nitrate and the ligands, 2-anilinoethanol (Hae), 2-(N-methylanilino)ethanol (Hmae), and 2-(N-ethylanilino)ethanol (Heae) in ethanol, have been studied by spectrophotometric, conductometric, and potentiometric methods.
Copper(II) ion reacts with Hae to form the complex ion [Cu(ae)]²⁺ (Cu²⁺: Hae: OHny=1: 1; 1) and the complex ion [Cu2(ae)3]⁺ (2: 3: 3). Copper(II) ion also reacts with Hmae to form the complex, ion [Cu(mae)]⁺ (Cu²⁺: Hmae: OH-=1: n: 1) and the complex ion [Cu2. (mae), ]²⁺ (2: n: 3) where n is above 10. The 1; 1 che1ate complex of Hae reacts with Hae to form[Cu(ae)(Hae)] in the prese: nce of a large excess of Hae, Copper(II)ion reacts with Heae to form the complex ion [Cu(eae)]⁺ (Cu²⁺: Heae: OH^-=1: n: 1) where n is above 40.
In Cu²⁺-HL system (HL: Hae, Hmae, or Heae), a small amount of the complex ion [Cu(L)]⁺ is formed in the presence of a large excess of HL. In this system, the, excess of HL acts as base.
In basic so ution these complexes lose ligands to form hydroxo co. mplexes. ln Cu²⁺-Heae system, Cu(NO3)2.3Cu(OH)2 is formed when the ratio Heae/Cu²⁺ is below 12.

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A simple and rapid fiuorescent X-ray analysis was proposed for the determination of trace amounts of copper, zinc, iron and nickel in magnesium and aluminum metals. The metal samples were dissolved in a mixture of hydrochloric acid and nitric acid and diluted to definite volume with water. After addition of selenium as an inner standard to an aliquot (less than 50 /ug of each copper, zinc, iron and nickel) of this solution, the pH was adjusted to 3 with sodifim acetate and hydrochloric thcid. To the solution, 5 ml of O.2% ammonium 1-pyrrolidi nyldithiocarbamate (APDC) sohisiion was added, and the precipitate of APDC complex was coliected on a membrane filter. After drying of the precipitate, the intensity ratios of fluore scent K. X-ray of each element to that of selenium were calculated referring to the calibration curves, which were linear up to 50ug of each element. The coefficients of variation for ten determinations were O.38, 1.62, 1.11 and O.62% for 25ug of copper, zinc, iron and nickel, respectively. The apalytical results for each element in magnesium and aluminum samples by the proposed method showed agreement with the results obtained by other methods.

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A sensitive coloration reaction of copper(II) with 1-naphtaldehyde 2-benzothiazolylhydrazone (NBTH) and pyridine has been studied to utilize the colored complex of copper(II), NBTH and pyridine for the spectrophotometric determination of microgram quantities of copper.
The ternary complex, Cu(II)-NBTH-pyridine, was found to be extracted quantitatively into benzene in the pH range of 6.9-9, 7. The extracted complex was stable and had an absorption maximum at 422 nm. The molar ratio of copper to NBTH was confirmed to be 1: 2 by using the continuous variation method.
A linear relationship was found between the concentration of copper and the absorbance. The molar extinction coefficient and the sensitivity for log(Io/1)=O. OO1 level were 4.8 X 104l/mol, cm and 1.3 X 10-3 ug Cu/cm2, respectively.
Several ions such as silver(I), cobalt(II), chrornium(III), iron(III), mercury(II), thiocyanate, tartrate and citrate with the determination. But silver and mercury could be eliminated by the addition of potassium chloride and potassium iodide as a masking reagent, respectively.
Recommended procedure for the determination of 0-10 ug of copper was as follow; take the sample solution containing up to 10 ptg of copper(II) in a 50 ml separatory funnel. Add 2 iinl of 10% pyridine solution and 1 ml of phosphate buffer solution (pH 7.0), apd theguamake the final Volume of the aqueous phase to 30 ml. Add 10.0 ml of a 2.0 X 10-4mol/l NBTH solutien in benzene and extract the coinplex by shaking the two phases for 20 minutes. Transfer the organic layer into a 50 ml stoppered flask containing about l g of anhydrous sodium sulfate. Measure the absorbance of the extract at 422 nm against the reagent blank.

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In the series of our investigations (Ref.1)-3 on countercurrent continuous gas chromatograph for binary system, it was found that the previous apparatus had a high performance, but it was of no practical use because the two stage operations were needed for the separation of the marked compound from the multi-component system.
New countercurrent continuous gas chromatograph (Fig.1), which was suitable for the purification of the marked compound, was devised by the authors. This apparatus was cosisted of the topper (11 mm i. d. X 1800 mm glass tube Packed with Naniwa Pack No.1), the separation column (17 mm i. d. X 1800 mm glass tube packed with Naniwa Pack No.1) and the stripping column (17 mm i. d. X 2200 mm glass tube packed with Naniwa Pack No.1). The liquid and the carrier gas fiow countercurrently at each column, and the sample which is the multi-component system is introduced continuously from the middle of the topper by the pump. At the toppe; the compounds which have smaller partition coemcients than that of the marked compound are separated from the multi-component system, at the separation column the marked compound is separated from the remains, and the compounds with the larger partition coefficients than that of the marked compound are purged from the liquid at the stripping column. As a result of these processes the marked compound can be purified.
The separation conditions were investigated, , and the equation of the maximum feed rate for the multi-component system was derived. On the separation of cyclohexane-benzene-toluene (1: 2: 1) system etc., using PEG 400 (20-60 ml/hr) as a liquid and nitrogen gas (2.60-12.0l/hr) as a carrier gas, eacch component was purified upper 99% (Table 4). lt was indicated that this apparatus approached to the practical use.

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The liquid chromatographic separation of some coumarins by a column of porous polymer in methanol was investigated. The retention times of 34 coumarins (in Tables 1, 2 and 3) were measured under the following operating conditions: column, 6mm, i. d. X 50cm glass column packed w ith Hitachi gel 3010; mobile phase, methanol; flow rate, 60ml/hr; temperature, 34.50C; detector, RI or UV.7-Hydroxycoumarin and its derivatives were satisfactorily separated in the following order: hydroxy-, acetoxy-, methoxy- and benzyloxy-coumarin. Moreover, this method was applied to the separation of coumarins in a erude product of methylation of 6, 7dihydroxy-4-methylcoumarin.2-Methoxychromone and 4-methylcoumarin derived from 4hydroxycoumarin by methylation was also separated.

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The γ -radiation-induced radical addition reactions of such ethers as tetrahydrofuran, 1, 4dioxane and diethyl ether to such Polyfluorocyclobutenes as (CF2)2CH=CC1(1), (CF2)2CF=CC1(2) and (CF2)2CH=CF(3) were studied.
In the case o f(1) or (2), the attack of ether radicals Z to the cyclobutenes occurred exclusively on the=CH or=CF, respectively, of the unsymmetrical double bond, yielding the corresponding 1: 1 adducts, while in the case of (3) the radicals attacked either the=CH or=CF, yielding the two isomers, (CF2)2CHFCHZ and (CF2)2CH3CFZ.
The ratio of the two isomers varied markedly with the structure of ethers.

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The spontaneous polymerization of Methylglyoxal (1) was studied by means of NMR spedtroscopy at 20C. The reaction rate increased by the addition of water or acetic acid, and also by use of quartz tubes in comparison with pyrex tubes. These reslts seemed to indicate that the spontaneous polymerization of (1) proceeded by cationic mechanism.
The structure of the hard glassy polymer (2) which was qbtained by spontaneous polymerization of (1) was studied by means of IR, NMR and Mass spectrosbopies. lt was found that (2) contained very small amounts of the aldol type polymer (2), but considerable amouts of the polyacetal type polymer which was linked not only by aldehyde group but also by keto group.
(2) was depolymerized by the addition of water or heating, and was easily ledit to (1) by the reactions with acids or bases.

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The peroxide-and irradiation-induc6a addition reactions of alky1enzenes (toluene, xylene, m-xylene, o-xylene, P-chlorotoluene, P-methoxytolu, ene, ethylbenzene, cumene)to hexafluoropropene were carried out.
The corresponding adducts, X-C6H CHRCF CHFCF3(2), were obtained in good yields together with a small amount of the other isomers, X-C6H CHRCF(CF3)CHF2(3) which were formed by the radical attack on the opposite side of the olenic bo: nd, No adduct was produced in the case, f cuiene. The relative reactiliy of the substituted t1uenes X-CH CH3, was determined by competitive reactions as follows;
X; pCH30 CH3 CH3 H o - CH3 C1
The trend shows that electron-donating groups favor the addition reaction. The corresponding styrene derivatives (7) were synthesized by dehydrofluorination of (2) with an alcoholic potassiumhydroxide.

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The reaction of isocyanuric acid with acrylonitrile in dimethylsulfoxide by the use of triethylamine as a catalyst was investigated under various conditions, and assuming the reaction, proceeds in terms of a three-step consecutive-competitive second-order reaction of the following type
A+B→ C, A+C→ D, A+D→ E
three rate constants were calculated.
It was observed that the relative ratios of k1/k3 and k2/k3 were 4.2 and 2.3, respectively, which were slightly different from the values given as the statistical factor, This result can be explained in terms of the decrease in electron density of the nitrogen on the ring due to the interaction between cyanoethyl groups and carbonyl groups on the ring.
From the time-concentration curves, the reaction conditions to obtain bis(2-cyanoethyl)is ocyanurate and tris(2-cyanoethyl)isocyanurate in excellent yield were elucidated.

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Formation of N-substituted benzamides by the reaction of N-benzoylsaccharin (BS) with various amines was investigated. The reaction of BS with aniline in MEK at room temperature gave the ring-opened adduct, N-benzoyl-o-(N -phenylcarbamoyl)benzenesulfonamide (1 a), whereas that in high1y polar solvents or in other solvents with basic catalysts afforded Nphenylbenzamide (2 a). BS reacted with the amines having lower basicity and those having higher basicity form ring-opened adducts and N-substituted benzamides, respectively. The adduct (1 a). was converted into (2 a) accompanied by the elimination of saccharin by treating with base or by heating above its melting point. From these results, it can be concluded that the reaction proceeds via the formation of the adducts (3) by the nucleophilic attack of amines to endo-cyclic carbonyl carbon of BS.

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It is an important ground work to elucidate the structural difference of coal tar pitches and various petroleum heavy oil ends or asphaltenes in order to use these chemical materials more effectively. However, since the raw materials in question have high molecular weight and a wide range of varying structural components, only a limited amount of information concerning the actual structure of the raw materials has been obtained by presently available methods.
Thus, in the present paper, a new approach is proposed by which the structural analysis of such raw materials as mentioned above, including the analysis of the number of naphthene rings and branched parafilnic chains attached to condensed aromatic rings, has become attainable. This was accomplished by proposing appropriate hypotheses and utilizing such presently available data as elementary analysis (C, H, N, S, O), NMR, average molecular weight and density together with a partly modified Hirsch's structural analytical method. Four floating parameters" have been set up so that the constructed model is similar to the actual structure. Calculatiens of this method are carried out easily and inexpensively by a digital computer.
Two examples of hypothetically constructed models (Table 2) were calculated and satisfactory results were obtained.

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Decyl, dodecyl, tetradecyl, hexadecyl and octadecylcarbamoylimide of trimethylamine have been prepared in high yields (68 - 82%) from the corresponding long-chain fatty amines via isocyanates, semicarbazides and semicarbazonium halides.
The 1, 1, 1-trimethylamine-2-(long-chain alkylcarbamoyl) imides are generally hygroscopic white plates. They have carbonyl stretching absorption at 1610 cm-1, and are easily differentiated from the corresponding semicarbazides (ν c=o=1680 cm-1) and semicarbazonium halides (ν o=o=1710cm-1).
The decyl, dodecyl and tetradecyl derivatives are good at lowering the surface tension of aqueous solution to 30 - 35 dyn/cm (25 C).
The amine-carbamoylimides have Krafft point, and their aqueous solutions are, contrary to other aminimides reported before, basic (pH=8.91 - 9.48, 0.25 wt%).

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In the presence of selenium dioxide, guaiazulene (GA) condensed with unsymmetrical ketones to give 1, 1-di(3-guaiazuly) alkanones.
The guaiazulyl compound obtained by the reaction with acetone was identified as 1, 1-di(3guaiazulyl)-2-propanone on the basis of its NMR and MS data, though the 1, 3-di(guaiazulyl)2-propanone structure had previously been proposed by Treibs and Vogt.
The methine proton next to the carbonyl group in the condensation product showed a NMR peak at an extremely low magnetic field. The low-field shift(δ 6.89 - 7.86 ppm (CDCl3)) seemed to be due mainly to the ring current effect of the two guaiazulyl groups and the electron withdrawing effect of the carbonyl group.

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Dynamic viscoelasticity of poly(m-phenyleneisophthalamide) films which were drawn or heat-treated was measured. The temperature dependence curves of E" and tan & measured over a range from 20 C to 400 C, exhibited two dispersion peaks at ca.100 C and 300 C.
When these results were compared with the data of infrared spectrum and DSC for the films, it was found that the peak at 100 C corresponded to transition associated with the breakdown of intermolecular hydrogen bonding and the peak at 300 C to the glass transition.
As the dispersion peak at 300 C changed sensitively with drawing or heat-treatment, the reletion between this dispersion and the fine structure of the film was investigated. It was concluded that the behavior of this peak was not directly related to the degrees of crystallinity and the orientation of the crystalline part, but to the distribution density of crystallites acted as netpoint in network structure and to the extent of tension of the molecular chain in amorphous part. The problem was further discussed in comparison with nylon 6 fiber.

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The polymerization of cyclic dimer of ε -caprolactam in the presence of poly(ε -caproamide)with phosphoric acid catalyst was studied. There are many difficulties in the polymerization of cyclic dimer because of its low reactivity, high melting point (347 - 348 C) and a marked tendency to sublime above 200 C. These difficulties were overcome by the polymerization procedure using phosphoric acid as a catalyst to polymerize the cyclic dimer in a poly(ε -caproamide) melt.
The polymerization of cyclic dimer catalyzed by phosphoric acid proceeded according to the first-order kinetics and rate constant was directly proportional to the amount of phosphoric acid. The apparent activation energy of the catalytic polymerization with 0.50 wt% of phosphoric acid was 35.3kcal/mol.

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Condensation polymerization of N-alkoxycarbonylthio(thiocarbonyl)-DL-α -alanine (1) was crrried out in dioxane or acetonitrile by heating (1) and the effect of the alkoxyl group in (1) on the polymerization was studied. Methoxy, ethoxy, isobutoxy, benzoxy or phenoxy groups was used as an alkoxyl group. Poly (DL-α -alanine) was obtained by heating (1) and the reaction mechanism was estimated to be the same, irrespective of a kind of the alkoxyl group except phenoxy group. The rate of polymerization of (1) increased and the molecular weight of the polymer decreased as the bulkiness of the alkoxyl group decreased. It was concluded that the rate of polymerization of (1) was dependent on the stability of (1) based on the nature of the alkoxyl group.

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N-Alkoxycarbonylthio(thiocarbonyl)amino acids was synthesized from methionine having a hetero-atom in the side chain. N-Alkoxycarbonylthio(thiocarbony1)methionine polymerized to poly(methionine) in a high yield in a suitable organic solvent such as dioxane when the solution was heated. The molecular weight of the polymer obtained from the L-monomer was much 1arger than that from the DL-monomer. The molecular weight of the polymer was found to be greatly dependent on the nature of solvent, which was related to the solubility of the polymer formed. Similarly, poly(L-α -alanine) having a high molecular weight was obtained from N-ethoxycarbonylthio(thiocarbony1)-L-α -alanine by choosing a suitable solvent.

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Diesters containing 1, 3, 5-triazine ring ((1 a) and (1 b)) were prepared in dimethylsulfoxide (DMSO) by treating dicarboxylic acid and diphenylester with p, p'-bis (biguanidinophenyl) methane.
Polytriazinylamides (2) ware synthesized by copolycondensation of hexamethylenediamine with (1 a) and diphenyl adipate. Polytriazinylesters (3) were synthesized by copolycondensation of 1, 4-butanediol with (1 b) and diphenyl sebacate.
(2) had reduced viscosity O.4 - 1.4 dl/g in m-cresol and formed a hard flexible film. (2)became more soluble in methylcellosolve and DMSO with increasing 1, 3, 5-triazine ring content. Polymer melting temperature (Tm) gave the minimum values (240 C) at X=0.20 and above 330 C at X=0.40 - 1.0 as shown in Table 4.
The thermal stability was improved and specific gravity increased slowly from 1.14 to 1.25with increasing guanamine structure content.
(3) had reduce d viscosity 0.23 - 0.38 dl/g and formed a flexible film. (3) became slightly soluble in chloroform and readily soluble in DMSO and specific gravity increased with increasing 1, 3, 5-triazine ring content. Tm gave a curve of V-shape having a minimum value at X=0.40. The entropy of fusion of (3) (X=1) became much smaller than that of polytetramethylene sebacate (X=O).

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Since S, S'-diphenyl dithiocarbonate (1) which initiated the photochemical polymerization easily decomposed into benzene thiyl radical, (1) was allowed to react with cyclohexene to clarify the reaction mechanism.
Photochemical reaction of (1) proceeded by the scission of carbonyl-sulfur bond and the produced benzene thiyl radical reacted with cyclohexene. From the reaction products, the reaction mechanism was clarified. In this case, thiophenol which was believed to be absent in the reaction products was found in the reaction mixture.
The initiation and termination mechanisms of the photochemical polymerization by benzene thiyl radical were thus clarified from the reaction products of (1) with cyclohexene.

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Phenyl vinyl sulfide (1) was found to polymerize with ease photochemically. Hence, (1)was allowed to react in various solvents photochemically and the reaction products were examined to clarify the initiation mechanism.
(1) decomposed itself into benzene thiyl radical contrary to the excited biradical initiation of styrene. The produced benzene thiyl radical initiated the radical polymerization of (1)similarly to the polymerization of styrene by benzoyl thiyl radical made up of dibenzoyl disulfide.
From the reaction products, the initiation and the termination mechanisms by benzene thiyl radical were estimated, but the chain transfer reaction was too complex to clarify its mechanism.
The photochemical reaction of 1, 1-bis(phenylthio)ethylene was also carried out and the similar reaction products and polymer were obtained.

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The polymerization of methylated styrenes initiated by AIBN was carried out in benzene in absence and presence of N, N-dimethylaniline (DMA). In the case of p-methyl-, p-ethyl-, 3, 4-dimethyl- or 2, 4-dimethyl-styrenes, the rate of polymerization (Rp) increased and then, after passing a maximum, decreased, with increasing concentration of DMA. On the other hand, Rp of styrene, m-methyl-, p-t-butyl- or 2, 5-dimethyl-styrenes was independent of the presence or absence of DMA. These phenomena could be explained by considering that the hyperconjugation effect of methyl group of styrenes was stimulated by DMA. In order to investigate the exact mechanism of the stimulation, the propagation reaction of the vinyl polymerization via radical mechanism was discussed.
As a principal transitional complex in the propagation step of radical polymerization, (3a) was considered.

This consideration was found to be supported by the linear relationship between activation energy of the propagation step (Ep) and easiness of transfer of electron from radical end to monomer, which was expressed by [Ea(M)-Ip(R)], where Ea(M) is electron affinity of monomer and Ip(R) is ionization potential of radical. Ea(M) and Ip(R) were calculated by SHMO method.
Granting that (3a) is a transitional complex, the effect of DMA on the rate of polymerization of methylated styrenes could be explained well.

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Polymerization of styrene was carried out in the system of tris(triphenylphosphine)chlororhodium(I) (Rh complex)-Organic halide under a hydrogen or a nitrogen. Hydrogen showed greater effect on the polymerization than nitrogen. In the presence of hydrogen, the organic halides containing three or four chlorine atoms joined to a single carbon atom were found to be the most effective for styrene polymerization. From the kinetic studies of the polymerization of styrene in a system of Rh complex and carbon tetrachloride, over the lower concentration range of carbon tetrachloride, the rate of polymerization (Rp) was expressed by the following equation:
Rp=k[Rh complex]0.5, [CCl4]0.5, [Styrene]2.0
The apparent overall activation energy for styrene polymerization in this system was estimated to. be 7.5kcal/mol. From the above results and the results of the copoiymerization of styrene with methyl methacrylate, the polymerization of styrene in this systeni was found to proceed in terms of a free-radical mechanism.

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The copolymerizations of N-vinylpyridazinone (1) and N-vinyldihydropyridazinone (2) with acrylic acid (AA) were carried out in bulk or in dimethylformamide (DMF) at 60 C using asobisisobutyronitrile (AIBN) as an initiator, and results were compared with previous results for copolymerization of (1) and (2) with methyl methacrylate (MMA).
Monomer reactivity ratios and Q, e values were obtained as fellows: r1=0.75, r2=0.15, Q1=2.22, e1=-0.72 for (1) (M1)-AA(M2), r1=O.06, r2=O.10, Q1=2.05, e1--1.50 for (2)(M1)-AA(M2). When AA was used as a comonomer, the alternating copolymerizabilities increased and the Q and e values of (1) and (2) varied.
A sharp shift of ν c=o in the IR spectra of (1) to longer wave length was observed by the addition of a small amount of AA.
All these observations indicate that the copolymerizability of the pyridazinone with AA is controlled by the monomer-monomer interaction due to hydrogen bonding between the carbonyl group of the pyridazinone and the hydroxyl group of AA, which varies the conjugation ability of the pyridazinone ring.

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Thermal degradation of polypropylene under atmospheric pressure at 370 - 410 C was studied by using a continuous flow reactor, which was the same as that used for thermal degradation of high density polyethylene shown in the preceeding paper.
Rate studies on polypropylene degradation were made at the steady states. Two rates, i. e., formation of double bonds and volatilization of degradation products, were measured and plotted in Fig.4 as a function of degradation temperature. The activation energies of polypropylene degradation, as calculated on the basis of these two rates, were 61 and 60 kcal/mol, respectively.
Gas-liquid chromatography showed that volatile products at room temperatures consisted of H2 and C1 - C5 hydrocarbons, mainly of propylene and isobutene, having an average molecular weight of 41 - 44 (see Table 2). And less volatile oily products consisted of C5 - C28 hydrocarbons, identified by comparing their boiling points (retention values determined by chromatographing) with those of n-paraffins. As illustrated in Fig.7, peaks do not always appear at a multiple of three carbon numbers, e. g., at 6, 9, 11, 14 and so on. The boiling points of a series of branched paraffins and olefins which are the chain fractions of various sizes produced by the degradation of polypropylene, were estimated by Wiener's method, and are shown in Table 3. It was found that above mentioned peaks contained branched mono-olefins whose numbers of carbon were a multiple of three.
The average molecular weight of oily products and reactor contents, determined ebullioscopically, are plotted in Fig.8, and numbers of double bonds per molecule are plotted in Fig.9. Oily products were found to consist mainly of mono-olefins, while reactor contents mainly of di-olefis. n

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Copolymers containing carboxyl groups and sulfo groups were prepared, and their catalytic activities toward the hydrolysis of amylose and sucrose were investigated. Copoly (acrylic acidstyrenesulfonic acid) in which the ratio of acrylic acid unit to styrenesulfonic acid unit being greater than by a factor of up to 10 showed slightly higher catalytic activities than a mixture (polyacrylic acid-polystyrenesulfonic acid) in which the ratio of acrylic acid unit to styrenesul-fonic acid unit being the same as the copolymer. From the analyses of thermodynamic parameters for the reactions, it was assumed that the "concentration effect" due to the hydrogen-bonding interaction between carboxyl groups of the copolymer and hydroxyl groups of the substrate was negligibly small, even if it would exist. Such tendency was also true for the reaction catalyzed by copoly (methacrylic acid-styrenesulfonic acid) or copoly(acrylic acid-vinylsulfonic acid).
Consequently, it may be concluded that in the present reaction condition, i. e., in the aqueous solution within low pH unit, interaction between carboxyl groups of the copolymers and hydroxyl groups of the substrate was negligibly small, , at least with regard to its contribution to the reaction rate.

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The lattice constants of the palladium black and palladium supported on alumina-silica were measured by means of an X-ray diffraction with a newly designed sample holder.
Lattice constants for both α - and β -phases were obtained for the palladium black which contains hydrogen corresponding to the horizontal part of the sorption isotherm (Fig.2). On the other hand, neither the horizontal part of the sorption isotherm nor the X-ray diffraction peaks which are indicative of co-existance of the α - and β -phases were observed for the highly dispersed palladium (Fig.3).
It was also shown that the degree of the expansion of the lattice in the supported palladium was smaller than that in the palladium black.

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4-Octylcatechol (1 a), which is expected to give a solvent soluble melanin, was oxidized to the corresponding o-quinone (2). The quinone was trapped as 2-octylphenazine (3) and 5, 6-diacotoxy-8-octyl-1, 4-methanonaphthalene (5) by the reactions with o-phenylenediamine and cyclopentadiene respectively. A catechol dimer (7 a) was also prepared from (1 a). The quinone and the dimer are considered to be the intermediate in melanogenesis of catechol.

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Cohydrolysis and subsequent polycondensation of the organochlorosilane mixtures containing polyfunctional monomers at refluxing temperature on the interfaces of binary liquid layers were found to give the corresponding soluble polysiloxanes with polyfunctional units as structural constituents.
From a series of equi-molar mixtures of tri- and difunctional monomers, were obtained soluble polysiloxanes with the repetition of tetrasiloxane as the structural units.
Mixtures of PhSiCl3 and MePhSiCl2 with T/D ratio of 2 - 10 also gave soluble products with thermoplasticity.
Another series of mixtures containing SiCl4 as quadri-functional component were found to give soluble gum-like products when treated analogously.

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The Friedel-Crafts condensation of dibenzofuran with phthalic anhydride in nitrobenzene gave 2-((1), mp 206.5 - 207 C, 63.4%) and 3-(o-carboxybenzoyl) dibenzofurans ((2), mp 236 - 237.5 C, 1.2%). The former (1) was heated with anhydrous zink chloride to give 2, 3-(mp 303 - 304 C) and 1, 2-phthaloyldibenzofurans (mp 247.5 - 248.5 C). The structures of these products were elucidated by comparison with the authentic samples.

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