New industrial manufacturing processes to obtain block and graft copo l ymers were developed by using special organic peroxides. Synthetic scheme is shown in Scheme 1. Step ( 1)shows the process to obtain block copolymers. In this process, polymeric peroxides (PPO)which have several 0-0 bonds in a molecule are used. Polymeric peroxides excelling in safety and solubility were newly prepared. One of them, for example, is [C(O)C₄H₈C(O)-(OC₂H₄)₃-OC(O)C₄H₈C(O)-O-O-tBu] First monomer is polymerized with PPO to provide PM₁ having 0-0 bonds. Second monomer is polymerized with PM1 having 0-0 bo nds to get PM, -b-PM2 as shown in step( 1 ). Step( 2 ) in scheme 1 shows the process to obtain graft copolymers. A monomer having an 0-0 bond [e. g. CH2=CHCH20C(0)-0-0-tBu] is copolymerized with M1 and conventional initiator at a temperature below the decomposition temperature (about 100 °C) of the 0-0 bond and PM₁ having pendant 0-0 bonds is obtained. Second monomer is addition-polymerized to the pendant 0-0 bonds to get PM₁-b-PM₂. Polymerization results were shown in Table 1.
(I) +R-0-0 10M I P M, 0-0 PM, M 2 P M 1 P M, POLYMERIC PEROXIDE (2) C C M1 PM, Mz pm, =0-0-R PMz PEROXIDE MONOMER (3) Polyolofin Poloyl fin Extruder P M, Scheme 1 Synthetic scheme of block and graftcopolymers with polymeric peroxides and peroxide m o n o m e r s Table 1 Block and graft copolymerizatio n Monomer (1/1 wt) Polym e r p r o d ucts (wt%)V A c/St PVAc-b-PS, 84 PVAc, 6, PS, 10MMA/St PMMA-g-PS, 44 PMMA, 33, PS, 23
Vinyl polymers having pendant 0-0 bonds are thermally mixed in an extruder with polyolefins and Polyolefin-g-Vinylpolymer is obtained by the reactive-processing in which grafting efficiency is about 50%. Some applications, such as surface modification, polymer c ompatibilization and impact modification with block and graft copolymers were studied.

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A Series of dye systems which contain acetylenic bonds in triphenylmethane dyes (triphenylmethane dye ethynologs) were systematically prepared and their spectroscopic properties were investigated. In attempts to synthesize the his- and trisethynologs of triphenylmethane dyes, a new preparative method was found, which gives the derivatives of pyrylium salts. The reaction of acetylenic alcohols (i. e., the precursors of triphenylmethane dye monoethynologs)with several nucleophiles afforded merocyanine dye systems having aryl-substituted push-pull butadiene moiety. Novel near infrared absorbing derivatives of triphenylmethane dye ethynologs were obtained by intramolecular bridging or extension of conjugation on triphenylmethane dye ethynolop. The results of the investigations on their color (visible spectra), correlation between the structure and the electronic states calculated by PPP-MO method, and a few applications of some dyes obtained to spectrophotometric analysis are briefly summarized.

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Hydrogen storage capacity and electrochemical capacity were investigated on four types of rare earth based metal hydrides. The hydrogen capacities of metal hydrides obtained by PCT (Pressure-Composition-Temperature) measurements showed a good agreement with the electrochemical ones determined using an electrochemical cell. In the alloys studied, MmNi_3.8. Al_0.3Mn_0.4Co_0.5sh owed the greatest capacity while MmNi_3.5Al_0.8Co_0.7the smallest. Structural analysis using the Rietveld method was carried out for MmNi_3.5Al_0.8Co_0.7a nd MmNi_3.8Al_0.3Mn_0.4Co_{0, 5} The basic structure of both alloys was found to agree with that of LaNi₅ (space groups P 6Immm). It was also found that aluminum atoms coordinate to 3 g site. X-Ray diffraction and the Rietveld analysis data indicated that the a axis of MmNi_3.5Al_0.3Mn_0.4Co_0.5is longer than that of MmNi_3.5Al_0.8Co_0.7, whereas the c axis of the former is shorter than that of latter. This suggests that the length of a axis is one of the essential factors that determine the electrochemical capacity.

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By static and dynamic light scattering, were measured osmotic compressibility, static correlation length, and hydrodynamic correlation length of aqueous solutions of heptaethyleneglycol monotetradecyl ether (C₁₄E₇) as a function of concentration ranging from 1 x 10^-3 g rn/-' to 0.1 gm/^-1 at various temperatures ranging from 35 to 55 °C. To make a quantitative examination of applicability of scaling and screening concepts to micellar systems, the results were compared with those of semidilute solutions of polystyrene in t-decalin near the thetatemperature with the aid of equations proposed here on the basis of the scaling theories for polymer solutions. The following conclusions have been deduced: ( 1 ) The present micellar solutions are not in the asymptotic scaling region, but in the crossover region from the poor- to good-solvent regions. ( 2 ) Osmotic compressibility and static correlation length of the micellar solutions can basically be described by the equations presented here covering the critical and the tri-critical semidilute regions, in common with those of polymer solutions. '( 3 ) Molecular parameters in these equations obtained suggest increase in the statistical segment length with increasing temperature.

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A solution of aluminum chloride hydroxide (Al₂C 1(OH)₅.2.4 H20) was added to a suspension of synthetic fluorohectorite in poly(vinyl alcohol) (PVA) (2.0 g of PVA and 1.0 g of synthetic fluorohectorite) by varying the volume of the solution: the resulting final concentration of the salt was in the range from 0.15 to 0.89 wt%. - The mixture was aged at 60 °C for 3 d followed by washing, drying, and calcination at 500 °C for 2 h. Varying the concentration of an aluminum chloride hydroxide solution was found to result in a systematic alteration of the interlayer distance of synthetic fluorohectorite pillared with alumina. The interlayer distance increased from 8.9 to 19.3A with increasing resultant final concentration of an aluminum chloride hydroxide from 0.15 to 0.89 wt%. Varying the concentration of PVA solution was also found to result in a systematic alteration of the distance. In contrast, the distance of alumina pillared synthetic fluorohectorite prepared in the absence of PVA was independent of the concentration of aluminum chloride hydroxide, i. e., ca.9Å. It was estimated that the lateral distance of alumina pillared synthetic fluorohectorite decreased from 20 to 12Å with increasing interlayer distance from 8.9 to 19.3Å.
These findings and the simulation may lead us to conclude that the presence of PVA during pillaring and varying the concentration of aluminum chloride hydroxide are necessary for controlling both the interlayer distance and lateral distance of alumina pillared synthetic fluorohectorite.

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Chromium borides were prepared by solid state reaction between chromium and amorphous boron powder at 600 to 1500 °C for 2 h in an argon atmosphere. Seven kinds of chromium boride phases such as Cr₂B, Cr₅B₃, CrB, Cr₃B₄, Cr₂B₃, CrB₂ and CrB₄ were obtained from the starting materials with the atomic ratios B/Cr = O.1 0-2.94. The variation of the atomic ratio of the starting materials gave different product phases. With increased boron content, more boron-rich phases are formed, however the boride phase having the composition of the highest boride, CrB₆, which does not exist was not detected. The formation of Cr₂B began at 600 °C in boron-chromium mixtures with a large excess boron content (B/Cr=1.04and 2.15). Cr₂B and CrB₂ were obtained as a single phase at 1500 °C and 1400 °C, respectively, while, Cr₅B₃, CrB, Cr₃B₄, Cr₂B₃ and CrB₄ were invariably obtained as a phase mixtures for various atomic ratios in the starting material at temperatures from 600 to 1500 °C. However, when starting materials with the atomic ratio of B/Cr=1.04 were used, the CrB phase shows the strongest relative X-ray intensities among CrB and Cr₅B₃ at above 1400 °C. The optimal conditons for the synthesis of Cr₂B and CrB₂ were found to include a reaction time of 2 h, reaction temperature and the atomic ratios of starting materials: 1500°C, B/Cr=0.50 for Cr₂B, 1400°C, B/Cr=2.15 for CrB₂. The lattice constants of chro mium borides are as follows: Cr2B (orthorhombic): a=7.4021( 9 ) Å, b=14.7044 ( 4 ) Å, c =4.2614 ( 7 ) Å, v=463.82 ( 5 ) ų; Cr₅B₃ (tetragonal): a =5.4781( 4 )Å c=10.0920( 5 ) Å, V=302.85( 6 ) Å3; CrB (orthorhombic): a =2.9723( 1 )Å, b=7.8647( 5 ) Å, c=2.9303(3 ) Å, V=68.49( 9 ) ų; Cr₃B₄(orthorhombic): a = 2.9923( 4 ) Å, b=13.0 154( 9 ) Å, c=2.9493( 1 ) Å, V=114.86( 3 )Å3; Cr₂B₃ (orthorhombic) a =3.0182( 5 )Å, b=18.1300( 6 )Å, c=2.9513( 9 ) Å, V=161.49( 5 ) Å.; CrB₂(hexagonal): a=2.9728( 5 ) Å, c=3.0719( 4 ) Å, V=23.51(2 )ų.

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On the complex formation of chromium(III) ion with glycine it has recently been reported that glycinate is coordinated not only as a bidentate ligand but also as a unidentate through carboxylate ion. These investigations, however, have been carried out within weakly acidic or acidic media. The present paper is concerned with mainly the IR spectroscopic study on the structure of the chromium(II) complex in an alkaline solution where an excessive amount of glycine exists as ligand. The complex solution and the refernce solutions which included graded amounts of glycine were dried by lyophilizing and then IR absorption spectra of these solid residuals were measured by use of KBr pellet techniques. The measurement of IR absorption spectra of the complex itself, especially, the estimate for the number of moles of glycinate coordinated to one mole of chromium(M) was achieved by making use of the reference samples. The behavior of the complex on heating at 90 °C for 20 h was investigated by use of technique subtracting the IR spectra of the original complex (before heating) from those of the resulting complex. Simultaneously Van Slyke method and Kjeldahl method were applied to the estimate for the number of amino groups coordinated to chromium(III) ion.
The following re sults have been obtained on the composition of the complex in the alkaline solution and the stability of the coordination bonds to heating.
First, it was found that on the average, four of f ive glycinate ions are coordinated to chromium(III) as unidentate through carboxyhlate ion (Fig.5-B), and the remaining one is coordinated as bidentate (Fig.5-A).
Secondly, it was proved that the coordination bond between chromium(III) ion and amino group in glycinate was almost entirely broken through heating at 90 °C for 20 h. However, the coordination bond between chromium(III) ion and carboxylate ion still remained unbroken as the unidentate ligand.
Thirdly, it was found that by heating at 90 °C for 20 h the IR absotption bands due to carboxyl groups ‹CO₂-› in glycinate ions forming chelate rings are shifted to the other wavenumber positions characteristic of carboxyl groups in glycinate ions coordinated to chromium(III) ion through the carboxylate ion as unidentate ligand, i. e. the absotption bands at 1650 cm^-1 and 1380 cm^-1 are shifted to 1600 cm^-1 and 1400 cm^-1 respectively after heating.

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In order to determine small amounts of rare earth metal ions, a new flow injection and continuous flow system using 1, 10-phenanthroline (1, 10-Phen) chemiluminescent (CL) detection was developed. The proposed system is comprised of three flow lines at flow rate of 2.5 m //min each; the sodium hyroxide solution line, the surfactant and dye-sensitizer solutio n line and the hydrogen peroxide and/or sample solution line. Rare earth metal ion samples containing the mixed reagents of 1, 10-Phen and EDTA (H4edta) are analyzed by the flow injection method or by the continuous flow method. The 1, 10-Phen CL for the determination of rare earth metal ions is produced by a reaction of 1, 10-Phen and reactive oxygen species produced by a reaction of rare earth metal-edta complex and hydrogen peroxide in the alkaline solution, and enhanced by surfactant and dye-sensitizer. Typical europium 011Y s analytical characteristics for the proposed system are as follows. The lower detection limits are 2.0 x 10^-8 M (1 M=1 mol dm-3) in 20 ul injection volumes and 1.0 x 1 0^-8 M in 2.5 m i/min continuous sample flows. The magnitudes for the determination are 3.3 x 10^-7-1.0 x 10^-5 M by the flow injection method and 1.0 x 10^-8-1.0 x 10^-4 M by the continuous sample flow method. Analytical time required is Ca.12 s by the 20 al injection method. Relative standard deviations are 2.2% by the flow injection method and 1.7% by the continuous flow method in 5 repeated runs of the 3 x 10^-5 M euorpium solutions. Copper (II), the substance which may cause the largest interference to the europium CL intensity, did not interfer the intensity even by the 3 x 10^-7 M coexistence in the 3 x 10^-5 M europium solutions. The analytical properties for other rare earth metal ions such as samarium (III) showed the same tendency to those for europium. Coal fly ash was analyzed with the present system.

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The aggregate morphologies formed by heating 4, 4'-bis(3-decylureido)diphenylmethane (DUDM) in paraffinic mineral oil were observed by scanning electron microscope. The morphologies of DUDM were a mixture of fiber with tube-like shape and unchanged platelet under microscopic observation when heat treatment was carried out at 160 °C. Some of them were changed to helical rope-like aggregates by heat treatment at 180 °C. The width of these fibrous aggregates was 0.05-0.08 μm and the direction of twist of helices was both left- and right-handed.
The form ation of rope-like aggregates was influenced by a cooling rate after heat treatment. When a cooling rate was O.6 25 °C/min the resulting morphologies were not helical rope, but thin film and coagulations. Because the aggregate morphologies varied depending uponr the cooling rate it might be assumed that those of DUDM in oil at 180 °C were not helical rope, but thin and fine tapes.
The morphologic al variation to tapes occurred in the temperature range which phase transition did not exist. Such variations may be caused by increasing flexibility of alkyl chains.
The hardening behavior of DUDM grease under high temperature can be explained by the increase of surface area due to morphological change from platelet and tubules to thin and fine tapes.

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N-Chloramines [1] in ether or chloroform solution prepared by treating primary amine hydrochloride with aqueous sodium hypochlorite were allowed to react with trialkyl phosphites [3]. It was clarified that the Arbusov type reaction readily occurred to give N-su bstituted phosphoramidates 5 1 in 61, -75% yield with elimination of alkyl halides. The reaction of N¹-substituted-N²-chlorobenzamidines [8] with tribenzyl phosphite [3 c] yielded N¹-substituted N²-[bis(benzyloxy)phosphinyl]benzamidines [9].
Sodium salt of N-chlorocyanamide [12] reacted with trisubstituted phosphines in water to yield the corresponding N-cyanophosphine imides [13].

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Alkali and alkaline earth metal salts of 3-butenoic ac id were heated in the solid state at 190-300 °Cfor 2 h under reduced pressure. Oligomers were isolated as their methyl ester s after the reaction with diazomethane and were characterized by their NMR, IR and MS spectra. Methyl esters of oligomers were detected by their gas chromatography. Sodium 3-butenoate gave dimer: dimethyl(E)-2-octenedioate(5-Me) (13.1%), trimer: dimethyl (E)-5-(methoxycarbonylmethyl)-2-decenedioate (6-Me) (18.4%) and tetramer: dimethyl(E)5, 7-bis(methoxycarbonylmethyl)-2-dodecenedioate(7-Me) (22.2%) by the thermal reaction at 225 °C. These oligomers (5-Me-7-Me) are believed to be formed directly from 3-butenoic acid. In contrast, four different kinds dimers, dimethyl 1-hexene-3, 4-dicarboxylate(1-Me)(28.9%), dimethyl 4-methyl-2-pentene-3, 5-dicarboxylate (2-Me) (5.6%), dimethyl( Z)-5-methy12-heptenedioate (3-Me) (9.5%) and dimethyl(E)-5-methy1-2-heptenedioate (4-Me)(17.2%) were obtained at 300 °C. These products (1-Me-4-Me) were regarded as the result of thermal dimerization of two molecules of crotonic acid, or crotonic and 3-butenoic acid. Potassium 3-butenoate was less reactive below 200 °C. However, over 250 °C 3-Me, 4-Me and 5-Me accompanying few amounts of 6-Me and 7-Me were obtained. Although alkaline earth metal salts gave very few amounts of dimers below 225 °C, heating over 250 °C mainly gave 2-Me, accompany 3-Me and 4-Me. The sodium salt maintained its crystalline state throughout the reaction. On the other hand, the salts of alkaline earth metal rapidly became amorphous as the oligomerization proceeded. t Thermal Oligomerization of Metal Salts of Unsaturated Carboxylic Acid in a Solid State. X.

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The hydrolyses of electron-accepting esters catalyzed by electron-donating azoles were investigated.1, 2, 3-Benzotriazole accelerated the hydrolysis of 1-naphthyl 3, 5-dinitrobenzoate in the pH range of 7 to 11, whereas the hydrolysis above pH 12 was retarded by the azole. The retardation was attributed to the formation of a charge-transfer complex between the ester and the anionic deprotonated 1, 2, 3-benzotriazole the nucleophilic attack by hydroxide ion on the ester is inhibited by the formation of the anionic complex. This inhibition is expected to take place over all the pH region above neutrality; therefore, the acceleration by the azole below pH 11 can be ascribed to bimolecular nucleophilic attack of free 1, 2, 3benzotriazolide anions on the free ester molecules that overrides the inhibition. The kinetics is expressed by a hyperbolic function which is similar to that for the Michaelis-Menten mechanism in enzymic reactions; however, this catalytic reaction is explained by the “nonclassical”Michaelis-Menten mechanism proposed by Menger.

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Several tripeptide aldhydes related to N-acetyl-L-leucyl-L-leucyl-L-norleucinal(A), having neurite-extension activity toward PC 12 cell lines, have been prepared. The most potent analog, approximately 50 times as active as A, was N-benzyloxycarbonyl-L-leucyl-L-leucylL-lecuinal. A degree of activity is likely to be related largely to the hydrophobicity or bulk of the N-terminal substituent of peptide derivatives and the side chain of a-amino aldehyde.

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Four poly(L-glutamines), i. e., poly[N5-[(R, S, and RS)-1-(1-naphthyl) ethy1]-L-glutamine](P(R)NELG, P(S)NELG, and P(RS)NELG) and poly[N5-(1-naphthylmethyl)-L-glutamine](PNMLG), were prepared from poly (L-glutamic acid) and corresponding amines using dicyclohexylcarbodiimide and 1-hydroxybenzotriazole as condensing agents. Their secondary structure and side-chain orientation were examined in solution as well as in film. P(R)NELG, P(S)NELG, and P(RS)NELG in dioxane solution gave strong circular dichroism (CD) signals in the '13, absorption band of the naphthalene chromophore. P(R)NELG, which gives the strongest CD signal, exhibited little excimer emission in its fluorescence spectrum, suggesting that the side-chain naphthyl chromophores in P(R)NELG are rigidly oriented with respect to each other along the peptide main chain. In film, P(S)NELG and PNMLG, while showing macroscopic anisotropy, gave strong CD singnals that split into positive and negative peaks in the 'Li, absorption band, suggesting that during film formation the naphthalene chromophores are so oriented that their 'L a transition moments undergo exciton interactions. The Amax values of excimer emission from P(R)NELG, P(S)NELG, and P(RS)NELG films were all around 360 nm, which is ca.20 nm shorter in wavelength than that of PNMLG film, i. e., 380 nm. These results suggest that chromophore orientati on can be regulated in solution and in film when chromophores are introduced to side -chains of poly (L-glutamic acid) through amide bonds.

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The regeneration of activated carbon loaded with nitrobenzene (N B) by supercritical carbon dioxide was studied. Supercritical carbon dioxide was introduced to the extraction cell packed with NB loaded activated carbon, and the fluid containing extracted NB was passed through heigh-pressure flow cell for spectrophotometry, and then was carried to a pressure reducing valve. The pressure reduced fluid was carried to a glass trap for collection of precipitated NB, and to a gas meter for measuring the volume of carbon dioxide used.
The ultraviolet and visible spectra of NB in supercritical carbon d ioxide were similar to that in hexane soltuion. The spectrum of aqueous solution of extracted NB precipitated in the glass trap was the same as that of the reagent NB used for initial loading. It was estimated that NB extraction was not accompanied with chemical change. The fractional regeneration calculated from the specific surface area of regenerated activated carbon measured by N₂ adsorption was smaller than that calculated from NB amount adsorbed from aqueous solutions. Above the, pressure of 200 kg/cm², the fractional regeneration increased as temperature increased, but below 150 kg/cm², the fractional regeneration decreased reversely as ternperature increased. The phenomenon was considered to be caused by the reversal of the effect of temperature on the solubility of NB in supercritical carbon dioxide. t Separation of Chemicals by Supercritical Fluid. I

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The purpose of the present work is to study the feasibil ity of the production of active carbon from wlanut shell, which is an agricultural by-product of relatively large quantity and low price. The walnut shell was carbonized first, then activated by steam. The effects of activation conditions on the characteristics of the active carbons obtained were experimentally investigated. The results are as follows.1) From all the raw materials employed, carbonized material having a relatively uniform macro-pores could be produced, and these are rich in macro-pores of 1.0-2.5 x 10^-6 m in radius.2) Active carbon obtained from the steam activation process showed the maximum YSg-value (Samax) at activation temperature 1173 K (Fig.6), and by correlating steam quantity and activated time, Samax of the active carbon determined (Fig.7).3) From measurements of BET surface areas, these active carbons were found to be rich in micropores of 2 x 10^-9 m in radius.4) Active carbon samples are found to possess high micro- and macro-pore volume and negligible mesoporosity, i. e. assumption of a bidisperse structure is correct (Fig.11).5) From meas urements of amount adsorbed of hexane-benzene solutions, these active carbons were shown to be more effective in the adsorption quantity than the synthetic zeolite 5 A (Table 3).
From these results, it seems that the walnut shell can be reutilized as the raw material of active carbon.

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The effect of reaction temperature on fine particle formation of basic yttrium carbonate by the homogenous precipitation method was studied. The average size of the particles precipitated at 77°C was 291 nm, but the size distribution was broad. The average size of precipitates at 87 °C was larger, 605 nm, and in addition, they had broader distribution in size. On the other hand, the average size of the particles precipitated at 97 °C was finer, 304 nm, than that of the precipitates at 87 °C and the size distribution was fairly narrow. The finer precipitates with narrow size distribution at 97 °C were possibly obtained due to more rapid generation of more plentiful precipitants caused by the decomposition of urea.

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N-Substituted 2-[(2-acylaminophenyl)thio]maleimides were treated with a weak base such as triethylamine to give 4-acyl-2, 3-dihydro-1, 4-benzothiazine-2, 3-dicarboximides in a fairly good yield via Michael type intramolecular cyclization. The chlorination of the dicarboximides, followed by dehydrochlorination, produced 4-acyl-1, 4-benzothiazine-2, 3-dicarboximides.2-[(2-Acetamidophenyl)thio]-N-methylmaleimides was treated with dilute hydrochloric acid to give 2, 3-dihydro-1, 4-benzothiazine-2, 3-dicarboximide. Antibacterial activity of those compounds was examined. All 2-[(2-acylaminophenyl)thio]maleimides exhibited good antibacterial activity against Gram-positive bacteria such as Bacillus subtilis and Staphylococcus aureus. All compounds tested were inactive against Gram-negative bacteria except for 2-[(2-acetamidophenyl)thio]-N-methylmaleimide and N-methyl-substituted 4 H-1, 4-benz othiazine2, 3-dicarboximide which were marginally active.

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The transient absorption spectrum of poly(ethylene 2, 6- naphthalenedicarboxylate) powders was measured by a microsencond diffuse reflectance laser photolysis method. The triplet absorption spectrum of the powders was observed around 460 nm, and the decay curve corresponded to a T-T annihilation process.

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