It was intended to establish the procedure of electrical conductivity measurement ef fine crystalline materials, uch as metal oxyhydroxides, which decompose at high temperature. The frequency dependence of the conductivity of unfired fine af-Fe20s in different degree of crystallinity was measured in the frequency range of dc to 30 MHz under various pressures of 90N 150kg cm2. The conductivity, 6, increases with increasing frequency, f. The ac conductivity, (=, d d being the dc c nductivity), is proportional to s(0.6 5 0.8)in the 100 7MHz frequency range. The disper ion of a.. is ascribed to the hopping of a d electron from localized ferrous ion to localized ferric ion. The frequency dependence of conductivity aRd dielectric constant is interpreted by regarding the compressed samples as the inhcmogeneous dielectrics consisting of fine crystalline materials with the above frequency dependent conductivity and of the intergranular gaps. Log a showed a linear correlation with the ratio, d, d', where d, is the true density of hematite and d is the apparent density of the compressed specimen. The frequency dependence of oi determined by the extrapolation of the linear log a vs. do d Plot t unity of the do d ratio is similar to that of the c nductivity of the sintered samples. di at 7 MHz increased with the crystallite size determined by X ray diffraction. These results indicate that di at 7 MHz is the electrical conductivity which reflects the inner structure of fine crystalline materials.

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Synthesis of potassium malonate from potassiym acetate, carbonate and, carbon monoxide has been studied kinetically under pressure in a molten potassium formate solution.
The initial rate of malonate formation is of the first order with respect to carbon monoxide pressure and mole ratio of acetate/carbonate in the charge.
Potassium carbonate reacted with carbon monoxide under malonate producing conditions to give a complex, which was decomposed in water into potassium formate and bicarbonate. The addition of malonate and formate, the reactyion products, into the system had no effect on the malonate formation.
Based on these results following mechanism has been proposed: potassiym carbonate reacts firs with carbon monoxide to form a complex as an intermediate, with which acetate converts into dipotassium malonate and potassium formate.
The rate equation and equilibrium constant given by apparent equilibrium constant of the complex formation and rate constants have been determined at 265, 280 and 300C to be respectively. The overall activation energy and apparent heat of complex formation are found to be 26.1 kcal and 19.6kcal, respectively.

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Propylene polymerization over TiCl₃-AlEt₃ catalyst in the absence of solvent have been carried out at various values of propylene pressure, P, molar ratio of AlEt₃ to TiCl₃, (A)and polymerization temperature. The kinetic curves(polymerization rate vs. time)are lower than those in the case with solvent and stationary has been represented by R R (K(A)jp K(A)P), were R is the stati nary rate in the case with solvent. The rate constant and activation energy(12 kca1 mo1)of propagation and the concentration of polymerizatio centers(1 x 1 2mollmo1-TiCI8)are same with those in the case with solvent. B t the average lifetimes of the growing chains(24 min)were shorter than those(40 min)in the case with solvent.

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Rheological properties of polyelectrolytes of the inorganic compound type have been investigated.
When the KPOs was dissolved in aqueous solution of NaPO3 or NaCl, there appeared two maxima in curves of viscosity and spinnability vs. time. From the relatienship between the maximum value and the concentration or the weight ratio (K Na), it has been found that when the molecular ratio of KPOs to added salt was 1 to 3, 4, 6, 8 and 12 mol, distinctive fea re were observed in the viscosity and spinnability. It is presumed that the viscosity and spin abihty of KPO3 aqueous solutions were closely related to the natureof non-counter io the contribution of branched chains, and especially to the coodination number of bound ions.
Kinetic studies of the degradation process of KPO3 aqueou solution showed that the relationship between velocity censtant k and 1 T (Arrhenius plots) con isted of two straight lines. From the lopes of the lines, the activation energy was evaluated to be 20rv40 kcal mol.

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The formatien of sodium pentacalcium sulfate scale (Na₂SO₄, 5CaSO₄, 3H₂) in the concen, tration process of the ion exchange membrane brine and its prevention by the help of various additives were studied. The formation zone of sodium pentacalcium sulfate was diseussed from the view point ef calcium sulfate transformation in the concentrated brine. Concentration tests were made by the use of a small evaporating apparatus at 75C, concentrating to the concentration-factor 1.3Av5. For the scale prevention were used various additives such as sodium hexameta-phosphate (SHP), sodium carboxyl-methyl cellulose (CMC), citric acid (CA), sodium citrate (SC), poly acrylic acid (PA), sodium poly acrylate (SPA), poly acrylamide (PAA), and Krilium (KM). These additives were introduced to the decarbonated brine, and the brine wa concentrated to the concentrationwfactor 2 with a small evaporating apparatu at 750C. Result are as following 1. The transformation of calcium sulfate in the concentrated brine was determined by the use of solubility of CaSO₄, CaSO₄1/2H₂O and CaSO₄.2H₂O which were measured by the Soga et al. and Egawa at al., and the results are shown in Fig, 2, lt was assumed that the formation zone of sodium pentacalcium sulfate existed between A and C line in Fig.2.2. The result of DTA, TGA and chemical analysis of the adhered scales showed that sodium pentacalcium sulfate was the main constituept of-scale (Fig.6). This phenomenon showed sodium pentacalcium sulfate scale was formed under the condition of No. 2 pan of triple-effect evaporator in the salt-manufacturing factories. 3. The comparison of calcium ulfate concentration in the concentrating brine with the calculated concentration value (Fig. 7), the analysis of constituent of adhered scale, adhesion rate of scale and change in heat-tran fer coefficient (Table 3) revealed that sodium hexametapho phate was the most effective for the inhibition of alcium sulfate deposition and the prevention of odium pentacalciun sulfate formation.

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Vavpor pressure and solubility of the ternary sulfuryl diamide-ammonium thiocyanateammonia system were investigated at O, 10, and 20C.
The vapor pressure was determined for the Iiquid ammonia solutions of NH2SOaNH NH4SCN mixture having a weight ratio of 3 1, 1 1, and 1 3 and the liquid ammonia solution saturated with respective solid components.
The vapor pressure of liquid ammonia is greatly lowered by the dis olution of NHaSO2NHx and NH4SCN. The liquid ammonia solution saturated with both solid shows the lowest vapor pressur among the ternfic ry solutions, having a vapor pressure of OC, 57 mmHg 10C, 70mmHg 20eC, 90 mmHg.
The solubility isotherms of the system NH2SO2NH2 NH4SCN NHs at O"C, 10"C, and 20"C are found to be simple. The pure NH2SO2NH2 and NH4SCN remains as solid phase. The isothermally invariant ternary solution saturated with both solid has a solubility of 379 g NH2SO2NH2 and 354 g NH4SCN at OC, 472 g NH2SO2NH2 and 419 g NH, SCN at 100C, and 640g NH2SO, NH2 and 510 g NH4SCN at 20"C for 100 g liquid ammonia respectivcly.

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Factors influencing the "bubble effect" were analysed for graphitei anode in the electrolytic cell of alkaline chloride by the merculy proce. Saturated NaCl birine waS electrolysed using a model cell equipped with graphite anode and mercury cathode under ipractical condition. For the factorial analysis of "bubble effect" an voltage drop due ito chlorine bubbles generated from the anode and thickness of bubble dispersion layer were measuredi.
From the results, it was found that current density and brine floiw rate were highly significant, the latter being an important hydraulic factor for the large capaciity, high current density, and lower voltage cell design.The most suitable flow ratei was above 4m3 hr unit cell width (m), where "bubble effect" was below 20 mV even at i100 A dm2.
As for anodic overpotential (rrA), it depended on some factersi, for example, comb-width of anode, current density and their interactions.
In consequence, data of the complicated electrolytic system were iarranged in terms of a praetical scale "apparent current density".
After plotting rrA against "apparent current density" on logarithimic graph paper, linear Tafel relation was obtained. Some deviations from regurality may be causedi by hydraulic effect of "bubble effect". The results obtained will be confirmed quantitatively by the pilot or practical cells.

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Acid formation constants, and stability constants fer divalent metal chelates of 1, 4, 7-triazacyclononane (2, 2, 2), 2, 2 diaminodiethylamine (2, 2), N (2-aminoethyl) 1, 3-propanediamine (2, 3), and 3, 3 diaminodipropylamine (3, 3) were determined by the pH titration at 25. OCC and ionic strength of O.1. A (2, 2, 2) coordinates with most metal ions alone in the facial configuration and forms three combined chelate rings. This restriction on freedom should contribute to the stabilities of its metal chelates as shown in Table 2. Besides, nickel, cobalt, zinc and cadmium chelates of (2, 2, 2) have the highest stabilities among triamine chelates ever reported. However, copper (2, 2, 2) chelate has slightly lower value than that of (2, 2) chelate, becau e copper(II)can only be coordinated with two nitrogen atoms of (2, 2, 2). On the other hand, the formation rates of (2, 2, 2) chelates are generally very slow, perhaps due to the comformational effect. Systematic comparison of the fermation constants with straight-chain triamine chelates has also been done in Table 1 and 2. Among three acid formatien constants of each triamine, Ka3 is mostly af ected by the Iigand size, K vaules of(2, 2)and(2, 3)chelates are nearly comparable and that of (3, 3) chelate falls respecting each metal, but KML, values are simply decreased in the order of (2, 2), (2, 3), and (3, 3), except copper and zinc chelates.

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Aluminum a refractory metal, can release little atom in air-acetylene flame and show no atomic absorption spectrum. A nitrous oxide-acetylene flame is used to increase its intensity. Al, in the presence of 8 hydroxyquinoline, has shown some atomic absorptionn in an airacetylene flame. An attempt was made to enhance the atomic absorption intensity of Al in an air-acetylene flame by the addition of a complexing agent to the solution to be aspilated. An appreciable enhancement has been obtained with complexing agents having co-ordinating N at6m. Much greater enhancement has beeR found. Lwith chelatting agents containing both co-ordinating N and O atoms. The enha cing effect in explained on the assumption as follow. WT the complexed Al is aspirated into the flame, an intermediate compound is formed and it prevents the formation of A120s, This intermediate compound readily dissociates to release Al alom at the flame temperature, without being oxidized. The complex chelating compound with N and O atom prevents the formation. gf A120.3 more effciently. The utilizatien possible to determine Al in Cu-alloy using air- makes is of the enhancing effect ef ligard acetylene fiame. Al in aluminum brenze casting can be determined with an accuracy estimating within about O.33%.

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The reaction of isoprene-CCl4 adducts (a mixture of 1, 1, 1, 5-tetrachloro-3-methyl-3-pentene(1) and 1, 1, 1, 5-tetrachloro-4-methyl-3-pentene(2)) with alkali was studied. This reaction proceeds step-wise and the reactivity of the adduct depends on the position of the methyl group towards the trichleromethyl group. 1-Carbomethoxy 4 methoxy-2-methyl-1-butene(9) and 1-carbomethoxy-4-methoxy. 2-methyl-1-butene(10) were obtained from (1), while 1, 1-dichloro-5-methoxy-4 methyl-1, 3-pentadiene(6) was obtained from (2). Furthermore, the model compounds such as 1, 1, 1, 5-tetrachloro-3-pentene(11) and 1, 1, 1, 5-tetrachloro-3, 4-dimethyl3-pentene(12) were synthesized and the reations were tested.
It is concluded that when the methyl group of the adduct is located at β-position towards the trichloromethyl group, the diene is converted to the chloroacetylenic compounds.

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The addition reaction of trimethyltin hydride to methyl-3, 3-dimethyl-1-cyclobutene carboxylate (1a) or 3, 3-dimethyl-1-eyclobutene carbonitrile(1b) in the presence of AIBN was studied. The B-adducts(2a, 2b), were found consisting of trans adduct (76%) and cis adduct (24%), were obtained in 57 and 50%e yields respectively. Further, the preparation of dimethylbromotin. derivatives of (2 a) and (2b) was tried. The NMR spectra of stereoisomer obtained in this paper were also discussed.

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Previously, it was reported that isopropyl β-acetoxy-γ-methylthiobutyrate(2) and β-methylthio-γ-butyrolactone(3)were produced by refluxing isopropyl β-chloro-γ-methylthiobutyrate (1) in acetic acid. From kinetic studies, successive reaction path of (1)-(2)-(3) was expected.
However, competition reaction path was not ruled out. Therefore, the reaction of (2) was checked. The formation of (3) was recognized in the reaction of (2) in acetic acid. And, (3) and isopropyl aetate were formed with the heating of (2) in toluene in the presence of sulfuric acid. Probable reaction mechanism was proposed and some of the rate constant was evaluated.

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The decomposition of 2-thenoyl peroxide in iodobenzene was carried out at 80C. In the presence of copper(II)chloride, iodopheny12-thenoates were produced. The isomer distribution and the partial rate factors suggested that the 2-thenoyloxylation reaction would proceed through the addition of a 2-thenoyloxy radical to an aromatic nucleus to give a cyclohexadienyl radical, fo11owed by rapid oxidation by copper(II)chloride. On the other hand, in the absence of copper(II)chloride the substitution of iodine by 2-thenoyloxy group took place to give phenyl 2-thenoate, which was not detected in the presence of copper(II)chloride. This substitution reaction is best explained on the assumption that the 2-thenoylexy group in the cyclohexadienyl radicals rearranges through an intramolecular migration of the carbonyl group to the carbon bearing an unpaired electron, and that phenyl 2-thenoate arises from a rearranged cyclohexadienyl radical with elimination of the iodine atom.

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In the presence of cupric chloride, the thermal decomposition reaction of di-β-naphthoyl peroxide with substituted benzenes has been investigated. The compositions of isomers and the relative rates for aromatic substrates indicated that the β-naphthoylexylatien proceeded by β-naphthoyloxy radicals possessing electrophilic properties. The partial rate factors for meta and para oxygenations might be correlated with the available σ⁺-substituent parameters according to the Hammett-Brown relationship. The straight line which was best fited to these points had a slope of -1.88.

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During the hydrogenation of benzaldehyde catalyzed by molybdenum trisulfide (MoS₃) at 120-230C under hydrogen pressure of 50 kg/cm², an appreciable amount of dimeric products, viz., benzoin, trans-stilbene and dibenzyl were obtained. ln order to elucidate the course of the reaction and the mechanism of dimerization, benzaldehyde and related intermediates were subjected to heat-treatment or hydrogenated under various conditions.
It was found that the dimeric products formed mainly in the absence of selvent, and in particular, trans-stilbene was noteworthily obtained as a main product under a relatively low pressure of hydrogen or at comparatively high hydrogenation temperatures. These results were quite similar to that obtained with the hydrogen-poor Raney nickel catalyst. Furthermere, during the hydrogenation of p-dimethylaminobenzaldehyde which scarcely underwent benzoin condensation, the corresponding dimeric product, 4, 4'-tetramethyldiaminedibenzyl, was obtained in the yield up to ca, 20%.
It was suggested that the formation of dimeric product might take place on the catalyst surface through radicals, and the chemisorbed-dihydroxy trans-stilbene might be a main intermediate in the formation of trans-stilbene.
During the hydrogenation of β-trithiobenzaldehyde at 230C, dibenzyl was obtained as a main product, and trans-stilbene or dibenzyl sulfides might be the main intermediates in the reaction. Whereas, benzyl mercaptan did not seem to play important roles in the formation of dimeric products under these conditions.
The hydrogenation reaction course and its mechanism were discussed, and the suggested path for the formation of dimeric preducts during the hydrogenation of benzaldehyde is illustrated in Fig.1, schematically.

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In the reaction of phenol with methanol over an active alumina catalyst to form hexamethylbenzene, it was found that pentamethylbenzene, tetramethylbenzenes, trimethylbenzenes, polymethylphenols and methylethers of polymethylphenols were also produced. Main by-products were pentamethylbenzene, 1, 2, 3, 5-tetramethylbenzene, 1, 2, 4-, 1, 3, 5-trimethylbenzene, 2, 3, 6-, 2, 4, 6-trimethylphenol, 2, 3, 4, 6-tetramethylphenol and pentamethylphenol. The amounts of these by-products increased with decrease in the amount of methanol in the starting materials and with lowering of the reaction temperature. Furthermore, pentamethylbenzene and tetramethylbenzene were readily converted to hexamethylbenzene under the reaction conditions, exclusively without formation of tetra- and tri-methylbenzenes. Tetra- and tri-methylbenzenes were probably converted from tetra- and tri-methylphenols, respectively, but the amounts of these methylbenzenes were smaller than pentamethylbenzene in the reaction products.
A plausible main reaction path for the conversion of phenol to hexamethylbenzene is the following: phenol 2, 6-xylenol. 2, 4, 6- and 2, 3, 6-trimethylphenol - 2, 3, 4, 6-tetramethylphenol pentamethylphenel pentamethylbenzene hexamethylbenzene.

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The autoxidation of cyclohexane and the decomposition of cyclohexyl hydroperoxide (CHP), which was regarded as an intermediate of the autoxidation, were studied in the presence of metaboric acid and orthoboric acid ester in various solvents.
It was found that the addition of the metaboric acid brought about considerable effects on the composition of the decomposition products, as well as an acceleration ef the decomposition of CHP (Table 1 and 2).
The decompositlon rate of CHP in the presence of metaboric acid was of storde and of zero-order with respect to the concentration of CHP and the apparent concentration of metaboric acid, respectively.
The rate constant k in the presence of metaboric acid in dodecane at 120-160C was as follows (Fig.2) k=3.31x10 11exp(-25.7x10 3/RT)min-1
The decomposition rates of CHP in aromatic solvents were faster than those in paraflinic solvents (Fig.1). Ortheboric acid ester showed no catalytic activity in the decomposition of CHP (Table 2).
Main products obtained by the decomposition of CHP in the presence of metaborie acid were cyclohexanol boric acid esters and small amount of cyclohexanone. Besides, alcohol boric acid esters and small amount of ketones, due to the oxidation of solvent, were also formed. A similar tendency was observed in the autoxidation of cyclohexane in the presence of metaboric acid (Table 3). It was considered that in the case of the autoxidation of cyclohexane in the presence of metaboric acid, cyelohexanol boric acid esters and active oxygen were formed by the reaction of CHP with metaboric acid.

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The structure and arbon chain distribution of the sodium vinylidene oSefin-sulfenate were investigated by mean of NMR, IR and GLC metheds.
As a preliminaly experiment, isomerization of 1-octene dimer elefin was undertaken for obtaining information about the structure and sulfonat mechanism of the sodium vinylidene olefin sulfonate. lt was found that dimer olefin was readily isemetized with sulfuric acid and main isomerization products were 2-octyl-2-octene and 2-hexyl-2-decene.
The double bond distribution of sodium vinylidene olefin sulfonate was analyzed by using the impreved ozonization-reduction-GLC method. Among widely distributed double bend position, d2N3 and d2pt-S sodium vinylidene olefin sulfenate were predeminant, arnounting to 54.5 and 24.4%, respectively (see Table 2). This result agreed with that obtained by isornerF zation of dimer elefin.
The position of sulfonic group in sodium vinylidene o1efin sulfornate was determined by using the combination method of decemposition of vinylidene sulfonyl chleride and GLC analysis. As vinylidene sulfonyl chlorides were converted into corresponding alky1 chlorides and olefin by a thermal decompositien, the position of sulfonic groups could be determined by the position of chloro groups. Under varieus conditions, the thermal decomposition at 160"C and for 1 hr was the best in this case (yield of alkyl chloride was about 60%). GLC analysis of these alkyl chlorides was carried out, and secondary alkyl ehloride was found te comprise about 62% of the total alkyl chlorides (see Table 3). This result suggested that larger parts of dimer olefin was sulfonated after isomerizatien of double bond.
Under more severe conditions, e.9., at 200C and for 2 hr, the vinylidene sulfonyl chlorides were decomposed into corresponding olefins. Fig.8 shows the gas chromatogram of decomposition product which indicates the characteristic pattern. These gas chrornatograms had been well resolved in terms of carbon chain length, giving successful determination of the carbon chain distribution in sodium vinylidene olefin-sulfonate (see Table 4).

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The thermal degradation of several polymers in air was studied by TBA (Torsional Braid Analysis) and IR spectroscopy. The samples are poly(vinyl chloride) (PVC), poly(acrylonitrile)(PAN), po1y(styrene) (PSt) and poly(methyl methacrylate) (PMMA), TBA measurement was carried out in the range of 200-350C and in the freguency range of 0.15-0.30 Hz. IR spectra of these polymers, degraded in air for 20 minutes, were also measured.
Relative shear moduli were plotted against the reaction time, and their initial slopes were fitted to the Arrhenius equation as function of temperature. From this analysis, the apparent activation energies were obtained as 24.7 kcal mol (170-250C) and 24.2kcal mol (250-340C)for PVC, 18.6 kcal mol(220-280 c)and 16.9kcal mol(280-340)for PAN, and 22.5 kcal mo1(initial stage)and 24.4 kca1 mol(1ater stage)for PSt. The IR, DTA and TGA measurements suggest that these changes of mechanical properties were associated with some chemical reactiens as follows. ln PVC, formation of C-C double bond by dehydrochlorination, crosslinking and oxidation are presumed in PAN, intramolecular cyclization by the reaction of nitrile groups and oxidation and in PSt, crosslinking by oxidation. lt was found that superposition procedure of the reaction time-temperature curves is possible for relative shear moduli of these polymers. ln the case of PMMA, change of mechanical properties assoiated with depolymerization was not observed.

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Interaction between sodium dodecyl sulfate (SDS) and poly(vinylpyrrolidone)(PVP) or poly (vinyl alcohol) (PVA) was studied by the measurement of conductivity at 30C. Equivalent conductivity, Aobs, of SDS decreased with increasing concentration of polymer, cp, in the case of low concentration of total SDS, cst. On the other hand, in the case of high concentration of this, cst(>CMC), Aobs, increased by the addition of PVP. These relations are shown in Figs.1 and 2.
It was found that the equivalent conductivity of PVA-SDS complex was of the same magnitude as that of SDS micelle (29 ohm^-1cm²eq.^-1), but that of PVP-SDS complex was slightly larger than that of SDS micelle, as show in Fig.6.
Assuming the complex to be a polyelectrolyte, and free SDS in the solution to be an added salt, it was found that the equivalent conductivity per bound SDS of the complex would behave quite similarly as that of a polyelectrelyte in a solution of a simple electrolyte, as shown in Figs.6 and 7. lt was, therefore, concluded that the complex could be considered as a polyelectrolyte.

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N-Substituted acrylamide derivatives containing Pyrrole nucleus were synthesized.
It was found that the rate equation of homopolymerization of PMA (R=H) was Rp=k[PMA]1.05, [AIBN]0.48 and that the chain transfer to PMA was not degradative. ln the copolymerization, the e value of PMA varied with polymerization conditions. Using styrene as a comonomer, the polarization of the carbonyl group of PMA was relieved due to dimerization through the hydrogen bonding so that the e value of PMA was negative (- O, 64). On the other hand, in the copolymerization with MMA, the dimerization of PMA was disturbed partially due to the intermolecular hydrogen bonding between PMA and MMA. Therefore the polarization of PMA was more increased to give a positive e value (+0.41), The hydrogen bending was confirmed by the red shift NH(pyrrole) in IR spectra.

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3-(2-Pyrrolylmethylenimino)propene-1 (PIP) and 2-diallylamino-methylpyrrole (DAMP) were synthesized and the copolymerizability of these monomers was examined. The parameters of the copolymerization of PIP and DAMP with acfylonitrile (AN) were obtaind as follows.
In the copolymerization of DAMP with fumaronitrile (FN), the maximum rate ef the copolymerizatien Rp(max) appeared at the lower concentration of DAMP in monomer feed. This can be explained by assuming that the degradative chain transfer to DAMP occurs remarkably at the higher concentration of DAMP. The copolymer composition DAMP/FN was 1/2, because DAMP is a diallyl monomer.
In the copolymerization of PIP with FN, Rp(max) appeared at the higher concentration of PIP. This is because the azomethine group of PIP may participate in the copolymerization as a propagating radical in addition to the allyl group of PIP. This assumption might be supported by the fact that the absorption of the vinyl group in IR spectra (δcH 990, 910cm^-1)remains slightly and that absorption ef the azomethine group in IR spectra (Vc=n 1640 cm^-1)is weakened.

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The effects of film thickness upon the graft polymerization of acrylonitrile onto poly(vinyl chloride) film ranging from 0.3 to 0.007 mm were studied by simultaneous irradiation technique with 2 MeV electron beam at room temperature.
The reaction rate was observed to increase with the reaction time at the initial stage, and then decrease in a following stage. A remarkable heterogenity of the graft concentration distribution was alse observed at the cross section of the grafted films.
These phenomena were shown to be caused by the change of the internal monomer concentration which is determined by the difference of the consumption rate of monomer in the films and the diffusion from the surface.

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Various macroreticular type resins were prepared by suspension copolymerization of many Vinyl pyridine derivatives with divinyl benzene in the presence of iso-octane as diluent. The adsorption capacities of these resins were greatly varied with the nature of vinyl pyridine ut monomer species and the ability decreased in the following order: poly(4-vinylpyridine)>poly-(2-methyl-5-vinylpyridine)>poly(2-vinylpyridine)upoly(5-ethyl-2-vinylpyridine). However, the variation in the pore structure of resin had little effect on adsorption capacity. The adsorption on porous resins was generally represented by BET type adsorption isotherm and the heats of adsorption were calculated as lo to 14.5 kcal/mol by use of Clausius-Clapeyron equa tion, larger than one of styrene-divinyl benzene copolymer, Amberlite XAD-2. The adsorption characteristic on the gel type resin was expressed as Henry s type adsorption isotherm. This fact indicates that sulfur dioxide is absorbed into the resin matrix and subsequently reacts with functional groups. lnfrared spectrum of poly(4-vinylpyridine) film exposed to sulfur dioxide gas had characteristic bands caused by SO₂-pyridine molecular complex formation at 1280, 1125, 534 cm^-1 and also indicated a band for SO₃^2- group (S-O stretching) at 940 cm.

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Water-soluble cationic polymers were prepared by the amination of the epoxy groups in pely(glycidyl methacrylate) (PGMA) with poly(ethylene polyamine). ln order to see the cationic flocculation effect of these polymers the kaolin suspension was used. The flocculation effect was studied by observing the supernatant suspension concentration in jar test, the sedimentation rate and sedimentation volume by the use of test tube. The best flocculation effect was obtained when PGMA(M.W.>60x10⁴)was treated with about 20mol polyethylenepolyamines (to epoxy groups) in acetene at 30-60C for 15-120 minutes. Diethylenetriamine, triethylenetetramine and tetraethylenepentamine gave similar effect. The suitable concentration range toward 500 mg/l kaolin suspension was 0.1-1.0ppm and the supernatant concentration at the optimum dosage after 2 minutes was below 40mg/l. The cationic polymers are most effective over the pH range of 2.5-8.5. The maximum rate of sedimentation was 5.8 cm/min, when the ameunt of the polymers was 0.010% of kaolin.

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In the complex formation between swollen poly(vinyl alcoho1)(PVA)membrane and copper(II)ion in aqueous solutionof copper(II)amine complex, the progress of the reaction into ligand substrate was invesgated by the cylindrical film roll method proposed by M. Sekido and K. Matsui as the method determing diffusion coefficent (D_(c)) of dyes in the multiple polymer membrane. The results show that in the system where complex formation occurs easily the combinationof Cu(II)ion with hydroxyl groups in PVA molecules has proceeded up to inner layers and the D_(c)', values are larger as compared with the system where the complex is more difficultry formed.

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Some polymers containing oxadiazelone ring in the side chain were synthesized by(1)polymerization of 2-phenyl-4-methacryloyl-1, 3, 4-oxadiazolin-5-one obtained by the reaction of 2phenyl-1, 3, 4-oxadiazolin-5-one with. methacrylic anhydride, methacrylic chloride or methacrylic acid, (2) polymer reaction of poly(methacrylic acid) with 2-phenyl-1, 3, 4-oxadiazolin-5-one, (3) polymerization of 2-phenyl-4-(1-azilidinylmethyl)-1, 3, 4-oxadiazolin-5-one prepared by the reaction of 2-phenyl-4-hydroxylmethyl-1, 3, 4-oxadiazolin-5-one and ethylenimine, and (4)polymer reaction of 2-phenyl-4-hydroxymethyl-1, 3, 4-oxadiazolin-5-one with pely(ethylenimine). Some properties of polymers containing oxadiazolone moiety were examined.
Further, amino acid containing oxadiazolone group, α-amino-γ (1, 4-oxadiazolin-5-on-2-yl)butyric acid was prepared from L-trglutamic acid.

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The reactionsof 2, 4-xylenol and 2, 6-xylenol with formaldehyde catalyzed by ammonia were studied by means of NMR spectroscopy and the chemical structure of the ammonia-resol formed was elucidated. Eight model compounds(see Fig.1)were synthesized and the chemical shiftsof their prgton signals in NMR spectra were iexamined(Table 1). It was found that the position of the 2, 6-xylenol was fairly more reactive than the 1position of the 2, 4-xyleno1. At the initial step of the reaction with 2, 4-xylenol, the tribenzylamino type compound(5 in Fig.1) was formed and it gradually changed into benzylamino-oxazine(3), while, with 2, 6-xylenol the tribenzy1-amine type compound was mainly formed together with a small amount of dibenzylamine(Fig.6). Further, methylol and dibenzyl-ether linkages were found in the product from 2, 4-xylenol, but methylol and methylene linkages were found in that from 2, 6-xyleno1(Fig.10). ApParent activiation energies of the reaction of 2, 4-and 2, 6-xylenol with formaldehyde were found tobe 17.9 and 18.2kca11mol, respectively(Flg.9).

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Previously, it was revealed that the nitrogen-containing compounds formed at the initial step of the reactions of 2, 4- and 2, 6-xylenol with formaldehyde catalyzed by ammonia showed a noticeable effect upon the reaction occurred subsequently, The present paper describes(I)a kinetic study of the reactions between the above xylenols and formaldehyde in the presence of oxazine and tribenzylamino type compounds dereived from the xyleftols, and (II) the products formed, and thier changes with time, examined by means of NMR spectroscopy.
Different behaviors of the nitrogen-containing compounds have demonstrated in the ondensation reaction, although the details are still obscure.

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The oxidation of propylene is known in industry as Wacker-process. lt is a consecutive gas liquid reaction, including fast reversible reactions.
The reaction, occurring in a stirred vessel with a flat gas-liquid interface at 25-v450C in the diffusional region, was studied from the standpoint of the chemical absorption theory.
The rate-determining step for the reaction was investigated in terms of the observed chemical absorption rates obtained over a wide concentration range of cupric chloride and was found to be carbonylation reactien.
The observed chemical absorption rates of propylene were analyzed on the basis of the chemical absorption theory of pseude m th-order irreversible reaction, and the carbonylation reactions were found to be first-order with respet to propylene or palladous chloride and to be reciprocal to first-order to chloride ien zero-order to hydrogen ion.
The rate constants were determined from the experimental data and analyzed en the basis of the chemical absorption theory for consecutive reversible reaction.
The mechanism for carbonylation reaction was studied by using the overall reaction order and the observed chemical absorption rates of propylene.

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Under extreme conditions at high pressures up to 60 kbar and high temperatures slightly below the melting points in the solid state, the polymerizations of cyano groups in dinitriles have been investigated. This paper describes the reactivity of glutaronitrile, adiponitrile and dimethylmalononitrile.
As in the case of malononitrile and succinonitrile reported in the previous paper, ghtaronitrile and adiponitrile were found to give polymers with carbon-nitrogen conjugated chain in the solid state.
On the contrary, dimethylmalononitrlle, which has no α-hydrogen, is hardly to polymerize. This fact indicates that the existence of α-hydrogen plays an important part in these reactlons. When a small amount of water was added, dimethylmalononitrile was polymerized and simultaneously, hydrolysis occurred slightly. From these facts the polymerization of cyano groups in dinitriles are consideTed to be initiated by the Thorpe type mechanism.

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The methods were developed for the decompesition of fluoropolymers and for the subsequent analysis of fluorine in them.
Decomposition was accomplished by heating the polymer in the K₂CO₃ capsule in an electric furnace at 600C for 30 min.
The K₂CO₃ capsule was prepared from casting molten salt in a carbon die.
The fluorine, changed into KF, was dissolved in water and determined by using a fluoride sensitive electrode.
The method was rapid and simple and was applicable to the routine fluorine analysis of organic compounds containing fluorine.

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The effects of shift reagent [Eu(DPM)₃] on the NMR spectra of alcohols, 3-phenyl-2butanol, 2-phenylpropanol, 3-phenyl-2-methyl-2-butanol, 3-methyl-2-butanol, 4-methyl-2butanol, and 2-methylbutanel, were studied. Two hydrogens er geminal dimethyl groups bonding to prochiral centers, the positions of which and the chiral center are 2 or 3 carbon atoms apart, showed remarkably different chemieal shifts by the addition of this shift reagent. C₄-Methylene protons and C₃-methyl protons of isoleucin methyl ester showed respectively different chemical shift from those of alloiso1eucin ester by the addition of this reagent. These shifts are interpreted in terms of conformational differences.

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The amount of trapped radical in radiation-irradiated poly(vinyl alcohol) (PVA) has already been measured quantitatively in terms of ESR by other workers. However, when vinyl monomer was graft polymerized onto irradiated PVA, some part of trapped radical seemed to become partially effective for the initiation of graft polymerization as the other part of trapped radical was inactivated by the side-reaction, e.g., a recombination of radical and an attack of residual oxygen in this system.
This paper deals with an elucidation of the above-mentioned fact. A DPPH radical was allowed to react with irradiated PVA under the condition similar to graft polymerization. The amount of trapped PVA radical which seemed to initiate effectively graft polymerization was estimated from the amount of consumed DPPH radical. This value was about a tenth of that obtained in terms of ESR.

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Water vapor permeability of poly(vinyl alcohol) (PVA) films modified by graft polymerizing by means of irradiation was measured. lt was recognized that water vapor permeability of PVA film was decreased by the grafting of styrene. Water vapor permeability of films whose graft percentage was greater than 400% was approximately equal to that of polystyrene fiim.
On the basis of the water vapor permeability data, decrease in water vapor permeability was found less effective in PVA films modified by graft polymerizing styrene than that of laminating films of PVA and polystyrene.

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A new method for recovering heavy metals in waste water was proposed. The reforming agent was used in this method, which combined with heavy metals to render them soluble and foamy. Air was then blown into the solution, and heavy metals, combined with reforming agent, were readily recovered on terms of a foamy shape during 10-20 minutes. This new method might solve many difficult problems involved in the conventional methods of treating waste water containing heavy metals.

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Nitration of hexamethylbenzene with benzoylnitrate by Willsttitter's method gave bis(nitromethyl) prehnitene. And, an aquedus alkaline solution of this bis(nitromethyl)prehnitene was poured into a hot dilute solution of hydrochloric acid, stirred for several hours under air or nitrogen atmosphere, and filtered to afford tetramethylphthalic anhydride in good yield.

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