Coin-type lithium secondary batteries using polya niline as positive electrodes have been developed and commercialized. The technical background of the development and fundamental concept of polymer battery designing were described. Advantages of polyaniline as electrode material were also discussed comparing with other conducting materials. Electrochemical redox reaction of polyaniline in nonaqueous electrolytes was pursued by spectroscopy and QCM (Quartz Crystal Microbalance) method. We concluded the chargedischarge reaction with two redox peaks in that system should be wholely described as electron acceptor type of doping-undoping reaction of poly(iminophenylene), which differed from protonation mechanism occured in aqueous system.
Polyaniline electrodes integrated with cu rrent collectors of stainless mesh were electrochemically fabricated directly from acidic solution of aniline. The reaction was controlled to prepare polyaniline composed of substantially only imino-1, 4-phenylene (IP) units, not to include quinonoid configuration of polyaniline nor benzidine. Polyaniline synthesized in the process hereby was aproved to be a new industrial chemical material without toxity by MITI of Japanese Government in 1987. The construction and per formances of one of the commercialized polyaniline-lithium secondary batteries (AL 2016) were described in detail. The capacity of the battery AL 2016was 3.0 mAh at charging voltage of 3.0 V, and 6.0 mAh at 3.5 V respectively. If more stable electrolyte is available the capacity would be increased twice or more.

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Effects of nickel starting sources on the catalytic activities and physic al properties were studied. The catalysts were prepared from five kinds of nickel starting sources by the impregnation method. Both hydrogenation of benzene and dealkylation of toluene were performed as the test reactions to elucidate the effects of catalytic activity. The nickel concentration profile in the silica sphere can be classi fied into two types. In the first type, the nickel atoms were uniformly distributed in the whole of silica sphere when catalysts were prepared from nickel nitrate or nickel chloride. In the second type, the nickel atom was concentrated in the vicinity of outer surface of silica sphere when using nickel acetate, nickel formate and nickel carbonate (Fig.1). The differences of nickel atom distribution in the silica sphere are responsible for the adsorption rate of nickel complex ion to the adsorption sites of the silica gel. Further, from TPR measurement, the second type catalys ts showed the strong nickel-silica interaction, but the first type catalysts were little affected by support (Fig.2). The catalyst prepared from nickel formate is more active than the other four catalysts (Table 1). The catalytic activities are found to be proportional to the degree of specific surface area of nickel particles on silica support (Table 2 and Fig.3).

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The objective of this per is the preparation of fine, sph erical Cu particles by spraypyrolysis technique. Effects of reaction conditions on properties, of Cu particles and the conductive pxoperties of thick films made from the Cu particles were investigated. Cu(NO₃)₂aqueous solution was atomized by ultrasonic vibration and heated under reductive atmosphere, H₂-N₂, by use of an electric furnace. Cu particles free from the oxides were produced above 600°C when H2 was above 6.2 vol%which was about 3 times of the equilibrium concentration (Table 1). Two morphological types of Cu particles, spherical and irregular-shaped, were observed (Fig.4). This morphological difference was attributed to the melting of Cu. Spherical Cu particles were formed when the particles were heated above m. p. of Cu for about 0.1 s or more (Fig.11). The number median diameter of spherical Cu particles varied from 0.3 to 1.3 pm in proportion to a cube root of Cu(NO₃)₂ concentration of the atomizing solutions (Fig.6), suggesting the formation of one Cu particle from one droplet of atomized solution. When the atomized solution was heated above ca.2000°C in rf-plasma flame consisting of H2-Ar, ultrafine Cu particles was produced, presumably from Cu vapor, in addition to the particles similar to these produced by furnace heating (Fig.7). From the above results, the formation routes for Cu particles were classified into three (Fig.10). Cu films prepared from the spherical Cu particles produced in the present study showed a low resistivity of 2.5 μΩ.c m (Fig.9)

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8-Quinolinethio1(I) reacts with zinc(II), cadmium(II), mercury(III), gallium(III), indium(III), thalliuma(III) and tin(II) to form the water-insoluble chelates with g reen fluorescence, and was use as a reagent for the fluorometric determination of these metal ions. The present communication reports the fluorescence properties of these metallo chelates, a summary of various conditions for the fluorometric determination of these ions and the factor for formatio n of these chelates. The general procedure for the fluorometric determination of metal ions was established as follows; To the sample solution, containing (0.1-10μg) of zinc, cadmium, gallium, indium, (10-40μg) of mercury, thallium, tin, added appropriate amount of 0.2 %(I) solution and 20%-sodium acetate or ammonium -chloride solution. Made up to about 10 cm' with water, and adjusted the pH to the optimum pH (Zn: 4.5, Cd: 5.0, Hg: 4.0, Ga 2.5, In: 1.5, TI Sn: 5.5 ), and extracted with 10 c m' of chlorofor m. Then, meas ured the fluorescence intensity against an uranin reference standard solution at the ordinary temperature. By using the reagent, (0.1-10)μg/10 cm³ of cadmium, indium, (1.0, -10μm/10 cm³ of zinc, gallium, (10-40)μg/10 cm³ of mercury, tin and (10-75) μg/10 cm³ of thallium could be determined within an error of 3%. The metal to ligand ratio in the chelate which prepared under the above mentioned conditions was fluorometrically determined by continuous variation method. The 1: 2 strong fluorescence chelate of zinc, cadmium and mercury and the 1: 3 stoichiometry for the gallium and indium chelates are observed. By the infrared absorption properties, force constants of these chelates were correlated to formation of their metal sulfides. From the fluorescence quantum yields and fluorescence sensitivity indexes, the fluorescence properties of these chelates were correlated to the affinity of sulfur atom and metal of these chelates and to the heavy atomic effect of the metal ions.

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The complex formation behavior of zinc 0, O'-butyl dithiophosphate (ZnDTP) and four kinds of “polyamine-polyisobutenysl uccinimides” (PIBSI) in liquid paraffin was studied at room temperature by thin-layer chromatography (TLC). A reversed-phase TLC method w as used for the determination of extracted ZnDTP in acetone phase after the complexation was carried out in liquid paraffin phase. The extracted ZnDTP was developed on a RP-8 plate with a water-acetone (45: 55 by volume) mixture solvent system.2, 6-Dichloro-p-benzoquinone mono (chloroimine) (1% in ethanol) was used as the coloring reagent for ZnDTP. The spots of ZnDTP were determined after 1.5 h followed by spraying the reagent at room temperature. Two wavelength reflectance method at 620 and 420 nm was used for the measurement of color intensity of the spot. The results showed that two types of complexes with the molar ratio of ZnDTP to amine of PIBSI were 1: 2 (Complex I) and 1: 4 (Complex II), respectively, were formed. The complex formation behavior of the complex IC was analyzed by the follo wing equation,
1/K'f= (αM.αLⁿ)/Kf
where K'f and Kf are conditional stability constant and stability constant of the complex II Then, αM. and αL, means,
αM=1+βm2[M]+βm3[M]²+ +βmn[M]^n-1
αL=1+ L2[L]+βL3[L]+ -+βLn[L]^n-1
βMn and βLn are association constants of n molecules of ZnDTP and amine contained in PIBSI, respectively. The number of the associations of ZnDTP and two amine molecules was two in any case, and any of two amine molecules in the four kinds of PIBSI behaved bidantate as ethylenediamine. All the value of the stability constants of the complex in liquid paraffin phase were determined as 4, -9 x 10⁶, and there are not so much difference between monosuccinimido types PIBSI which have primary and secondary amine and bis succinimido types PIBSI which have only secondary amine. The assoc iation constant of the ZnDTP in liquid paraffin was determined as 3--5x 10² from above equations. And two molecules amine of PIBSI shuold be behaved as one unit in liquid paraffin, the association constants of one unit contained in two molecules amine were 0.6-1.5X 10⁸ and 0.5, -7 x 10² for the mono- and bissuccinimido types PIBSI, respectively. So that, the association constant of the monosuccinimido types PIB SI was slightly large than that one of bissuccinimido types. The structures of the complex I and II were discussed, so that it assumed that both types of complexes have 6 coordinated octahedral structures.

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Agricultural chemicals, which contained sulfur or phosphorus, were analyzed by micro liquid chromatography with a flame photometric detector (FPD) equipped an electrospray burner. The chromatographic conditions: Analytical column was a O.5 mm in i. d. and 110mm in length packed 10 pm ODS silica geL Eluents were 40 vol% aqueous 1-propanol or 2propanol and its flow rate was 8 μl/min. Electrospray burner conditions: Applied potential between two electrodes was 2500--3000 volts.
The effluent from analytical column w as nebulized at narrow capillary nozzle attached to the column, and burned in hydrogen flame. The optimum working conditions of FPD: Flow rate of hydrogen for lower flame and upper flame were 72 mgmin and 109 mllmin, respectively, and flow rate of oxygen was 60 mi/min. The emissions of sulfur and phosphorus were detected by a photomultiplier through the 394 nm and 526 nm interference filters, respectively. The emission signal of sulfur was proportional to 1.8 powers of sample weight, and that of phosphorus was proportional to sample weight. The detection limit of MEP was 0.2 μg by emission of sulfur, and was 5 ng by emission of phosphorus.

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Performance of a new radial-flow column (Sepragen Corporation) was compared with that of a conventional down-flow column on separation of proteins in egg white. Further, a method for analysis of proteins in egg white was developed: Following results were obtained.
1) A rapid analytical method for proteins in egg white by high performance liq uid chromatography employed aminopropyl bonded silica was established, and the method was successfully applied to identify proteins in fractions separated by preparative scale chromatography.
2) In the case of soft packing material such as DEAE cellulose, the separa ble performance of the radial-flow column with large cross section at flow direction of eluent was superior to that of the conventional down-flow column with small cross section. Proteins in egg white were separated into 3 fractions; ovoglobulins containing lysozyme, ovomucoids containing ovotransferrin, and ovalbumin.
3) In the case of rigid packing material such as hydroxyapatite, the separable performance of the conventional down-flow column was superior to that of the radial-flow column since the down-flow column can withstand high pressure to pack up the packing material. Proteins in egg white were separated into 4 fractions. The fractions were eluted in the order with increasing isoelectric points; ovomucoids (3.9-4.3), ovalbumin (4.5-4.8), ovoglobulins containing ovotransferrin (5.5-6.6), and lysozy me (10-11).

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Intra- and inter-molecular hydrogen bonding of o-, m- and p-substituted anili ne derivatives was spectroscopically studied by using 'H-NMR, FT-IR, and Fl-MS. Aniline derivatives investigated were nitroanilines (NA), chloroanilines (CA), aminoacetophenones(AAP), Nitroacetanilide(NAA), 2-chloro-4-nitroaniline, 4-chloro-2-nitroaniline and 2-chloro-5-nitroaniline.
The solvent used in the 'H-NMR and FT-IR measurements was carbon tetrachloride, chloroform and chloroform-d, which hardly gave the solvent effects. The line-widths of 'H-NMR for protons of -NH2 of 0-NA, o-AAP and 4-chloro-2-nitroaniline were appreciably increased as temperature was reduced in the lower temperature region (-10-50°C) (The example for o-NA was shown in Fig.3). These results were interpreted as the impairment of cha rge symmetries of 1H-nuclei caused by the formation of intramolecular hydrogen bonding by one of the protons of -NH₂.
As for o-CA, it is suggested from the result of the temperature dependence of the linewidths of H-I-NMR that the intramolecular hydrogen bonding is not formed. These 'H-NMR results were supported by the FT-IR studies. In the case of o-NA and o-AAP, the value of (v_asN H-v_sy NH) increased in comparison with the corresponding m- and p-substitued anilines (by ca.30, ---60c m-1) (Table 1) respectively. On the other hand, m-NA, p-NA, m-AAP, p-AAP and CA gave the (v NH) peaks attributed to both monomers and dimers (Fig.4), suggesting intermolecular hydrogen bonding. Furthermore, by means of Fl-MS measurements, the dimers peaks associated in the inonized state were observed for m- and p-isomer of NA and NAA (Fig.5)

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Stereochemistry of C-3 hydroxyl group of hexahydrosantonins (HHS) (4), (5 ), (6), (7), (11), (12) and (13) obtained by reduction of, satonin (1) had been assigned by the comparison of molecular rotation, of each compound with its acetate. Since reexaminat i o n of their molecular rotation (Table 1) revealed that this method afforded amb i g u ous results in the case of HHSs, the authors tried tp; determine their stereochemistry by compar isono f their ¹³C-NMRlc hemical shifts with calculated values, and by Mosher's method, whi c h assigns the absolute configuration of alcohols.¹³C-NMR chemical shifts of cyclohexanols and decalin-3-ols have been examined in detail and stereochemistry. of the hydroxyl group has been known to give significant influenc e to the chemical shifts of neighboring carbon atoms. Comparison of ¹³C- chemical shifts o f HHSs (Table 2) with values calculated (Tabel 3) using parameters reported by Grover and Stothers, Schneider and Hoppen, and Senda et al. suggested that the stereochemistry of C-3 hydroxyl group in (4) is α-equatorial, that in (5) is β-axial and that in (13) is α-equatorial. These results disagree with those previously reported. In order to make an assignment of din-figuration of C-3 hydroxy l groups, each HHS was converted to R7 and S-a-methoxy- a-trifluoromethylphenylacetates (MTPA ester) and their 'H-NMR chemical shifts were compared.. According to Mosher's method, 4-methyl si gnal of R-MTPA ester of 3 S-HHS (R-S ester), is expected to appear at higher field than that of S-S ester, which is the case with (4). Since the relative relationship between the acid moiety and the alcohol of these esters, is equivalent both, in R-S ester and S-R ester, and R-R ester and S-S ester, respectively, C-3 of [5] has R configuration. These observations are accord well with the results from their ¹³C-NMR chemical shifts investigation.
By using these two methods, C-3 configuration of these seven HHSs was determined as shown in Fig. 1 and 2.

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When azoxybenzene (1) was warmed in 35% nitric acid (HNO₃-AcOH-H₂0) for 1 h at 80°C, 2-nitro-ONN-azoxybenzene (6) was selectively obtained in a 77.0% yield. Under the same reaction conditions, an equimolar mixture of 2, 2'-dimethyl-3-nitro-NNO-azoxybenzene (7α)and 2, 2'-dimethyl-3-nitro-ONN-azoxybenzene (7β) was found in the nitration of 2, 2'dimethylazoxybenzene (2). Similarly, an equimolar mixture of 4, 4'-dirnethy1-3-nitro-NN9azoxybenzene (8 α) and 4, 4'-dimethy1-3-nitro-ONN-azoxybenzepe (8β) was obtained in the nitration of 4, 4'-dimethylazoxybenzene (4) (Table 1).
_??_
The nitration of 4-methr1ONN-azoxybenzene (5 α) (α: β =2.4: 1.0) took place rapidly than that of 4-methyl-NNO-azoxybenzene (5β) (α: β=.0: 1.0) using 35% nitric acid (HNO₃-AcOH-H₂0) (Fig.1). Jn the nitration of (5 α), 4-methy1-3-nitro-NNO-azoxybenzene (9β) and 4-methyl-4'-nitro-NNO-azoxybenzene (10β) were found as the reaction productsy and the rapid isomerization from (5 α) to (5 β) and slower one from (5 β) to (5 α) were indicated in recovered starting 4-methvlazoxvbenzenes (Figs.2.3.4 and Table 2)
_??_
.66 El * IL T.1990 No 1On the other hand, 4-methyl-3-nitro-ONN-azoxybenzene (9 α) and (9 β) were detected in high α/p ratio along with (10 β) in the reaction of (5 β). The α, β-interconversion between (9 α) and (9 β) took place with laspe of time and the slow β, α-isomeric conver sion of (5 β) was also found under the reaction condition's (Fig.2, 3, 4 and Tabel2)
_??_
The isomerization of unsymmetrically substituted azoxybenzenes in dilute nitric acid seems to depend on an interaction of them with nitronium ion.

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Autoxidation of dimethyI 2-amino-1, 3-azulenedicarbocylate (1) at 120°C in HMPA or DMF for 72 h gave three major products (in 13% conversion). They were dimetyl 2-amino4-hydroxy-1, 3-naphthalene dicarbOxylate ( 2 ) (15% yield based on consumed (1), dimetyl 3-aminocyclohepta[ b ]pyran-2, 4-dicarboxylate (3) (15% yield), and dimethyl 2-amino-63-azulenedicarbgiulate, (4) (20% yield). The structures of these products were established by the spectroscopic (UV, MS, IR, and NMR) data Possible reaction pathways are suggested for the formation of (2) and (3). Y 71

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It was found that quinazoline derivatives were formed by the reaction of 2, 1-benzisoxazoles with 3-substituted 5-alkoxy-2, 4-imidazolidinediones. For example, N, 4-diphenyl-2-quinazoline carboxamide was obtained by heating the dioxane solution of 3-phenyl-2, 1-benzisoxazole and 5-methoxy-3-phenyl-2, 4-imidazolidinedione in the presence of titanium tetrachloride (yi eld 82%). The reaction may proceed by the t4 +2 jcycloaddition of 2, 1-benzisoxazole with 3-imidazoline2, 5-dione formed in situ from 5rnethoxy-2, 4-imidazolidinedione followed by the elimination of carbon dioxide.

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Thermal chlorinolysis of 1, 1-dichloroethane (ED) was carried out by means of the laboratory and pilot plant scale experiments.1, 1, 1 -Trichloroethane (MC) and'vinylidene chlor ide (VD), could be co-produced in fairly broad formation ratios by controlling the reaction conditions. Furthermore, if the chlorinolysis was conducted by feeding ED with MC, VD was formed in high yield. On the other hand, MC- was also`'procluced in high selectivity by recycling VD with VC to the hydrochlorination section. That is to say, MC and VD could be produced with an optional ratio by combining thermal chlorinolysis with liquid phase hydrochlorination. The results obtained from the laboratory experiments are summarized as kollows. ( 1)While the conversion of ED increased with increasing the molar ratio (Cl₂/ED), the selectivity into MC and VD decreased. ( 2 ) The yield of MC and VD (MD Yield) had a maximum at O.9 of the molar ratio. ( 3 ) The product composition could not be affected with the fee d rates of ED and chlorine. ( 4 ) The split ratio [100x VD/(MC+VD)] was changed in broad range with the reaction temperature. In case of pilot plant experiments, the thermal chlorinolysis of ED proceeded adiabatically according to the balance of exothermic chlorination with endothermic dehydrochlorination. Consequently, the reaction temperature was uncontrollable and was maintained at 460-480°C throughout the reaction. The chlorinolysis of ED with the tubular reactor gave higher MD yield than the vessel reactor. The split ratio showed the reverse relation. These results are explained on the basis of piston flow for the tubular reactor and perfect mixing for the vessel reactor. The MD yield was increased with increase of the molar ratio'and was decreased by increasing the reaction pressure. On the contary, the split ratio was increased with increase of the reaction pressure. It seemed to be reasonable that ED was more favorably converted into dichloroethylenes such as VD than trichloroethanes by reacting ED with chlorine radicals generated more under higher reaction pressure.

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In order to develop new utilizations of cresols in coal tar and coal liquids, oxidation of cresols in acetic anhydride was investigated. The methyl groups of cresols were oxidized smoothly in acetic anhydride with oxygen in the presence of transition metal acetates and certain bromides as catalysts to give acetoxybenzoic acid derivatives as main products, . The most active catalyst system was Co(II)-Ce(II)-NH₄Br. The proper ra nges of, concentration of metal acetates and molar ratio of the bromide to metal acetates were 2.0 x10^-2.6.0 x 10^-2 (mai/kg) and 2.0-3.0, respectively. Effects of reaction temperature, concentration of p-cresol (PC), and weight ratio of acetic anhydride to acetic acid on the yields of oxidation products were also examined. The oxidation of PC at 120°C gave p-acetoxybenzoic acid derivatives in about 90% yield. The oxidation of m-cresol (MC) and o-cresol (OC) was also ca rried out by the same procedure, giving the following order of yields of the corresponding acids; PC>MC>OC.

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Sorption heilayior of organic solvent vapors in the dry air on raw rubbers such as cispolybutadiene, cis-polyisoprene and acrylonitrile-butadiene copolymer coated on the surfa ce of piezoelectric crystals was observed by measuring the decrease (-ΔF)in the bas ic frequency of the crystals.
In the vapors of good, solvents such as toluene. for cisTpolybutadiene, . -ΔFs were proportional to the solvent concentrations, whereas in nonsolvents, i. e., methyl alcohol fo r cispolybutadiene, no changes in ΔFs at any, concentration were observed. Other combinatio ns of rubber/solvent have shown that the. sorption behaviore ?is in good agreement the results obtained by swelling experiments. In a system of acrylonitrile-butadiene copolymer4-b utanol, however, showed high adsorption behavior. This suggests that polar- pola. i interaction of polymers/solvents is important to observe the adsorption of organic solvents on th e polymer thin film.
Application of quartz crystal microbalance method- could be able to evaluate solvent power for polymer thin films which are coated on quartz crystal.

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Dialdehyde cellulose(DAC), developed as a chemical sorbent tor urea removal, was mounieu by the chitosan coating for the application to the conservative oral sorbent therapy toward the chronic renal failure. The objective of the modification is to obtain more stable sorbent for the wide range of pH change and to prevent from the undesirable binding with protein nutrients.
The prolonged periodate oxidation of h. olocellulose, prepared from saw dust, gave DAC with the dialdehyde unit content of 93%. The chitosan coating was performed by the vigorous stirring of the DAC suspension in 1% chitosan solution of methanol-acetic acid-water at room temperature for 24 h. The resulting 10% chitosan coated DAC showed far less elution (a 4%) than noncoated one to the buffer solution of pH 7.5. It remained 85% of the glucose unit as dialdehyde state, keeping a considerably high urea binding capacity of 8.6mg/g at 37>C after 24 h against 113 m g/d/ urea solution. Its selective binding for urea was demonstrated by the competitive reaction with far excess amount of albumin.

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The influence of addition of H₂0 on the hydrogenation of carbon monoxide by Co₂(CO)₈catalyst has been investigated under a syngas pressure of 1000 kg/cm2 in phenolic solvents. The addition of 7-20 vol% H₂0 to m-cresol or phenol solvent suppressed the formation of methanol and *as effective in increasing the catalyst activity and selectivity for ethanol(EtOH)formation. The addition of H₂0 showed a tendency to improve the selectivity for ethylene glycol (EG) formation. A Co₂(CQ)₈-H₂0-phenol catalyst system gave about 70% se lectivity to C2-oxygenated compounds (EtOH+EG) and high space-time yield of those compounds (164.0 g//.11). The role of H₂0 is discussed.

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Bromo-substituted aromatic amines were obtained quantitatively by passing a solution of aromatic amines in dichloromethane-methanol through a column packed with styrene polymerbound benzyltrimethylammonium tribromide. t Halogenation Using Quaternary Ammo n ium Polyhalides

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Ring-closure reactions of 3-phenyltiopropionaldehyde (1 a) and its methyl derivatives which were formed by the additions of benzenethiols to acrylaldehydes using acetonitrile as a solvent have been investigated. The reactions of ( 1 a) and its methyl derivatives with a variety of thiols in acetonitrile at room temperature provided 3-plienylthiopropionaldehyde hemithioacetals (2). The reaction of (2) in the presence of sulfuric acid in acetonitrile afforded the corresponding 4-arylthioand alkylthiothiochromans (3 a-i) in good yields.

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Flotation of aminoacetic acid (glycine, HL) by complexing with iron(III) was investigated in a cell (20 cm x 2.5 cm I. D. ). Recovery of 1.0 x10^-3 mol.dm^-3 of glycine was 97% by cornplexing with the equimolar concentration of iron(1ll) using 3.25 x10^-3mol. dm^-3 of dodecylammonium acetate (DAA) as a surfactant at pH 6.0. It seems that the flotation of glycine proceeds through the formation of the ion pair RRFeL(OH)- where R and n denote the cation of DAA and its mean number, respectively. This flotation was found to be applicable to recovery of glycine in a waste solution at a manufactory of dried bonito.

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