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Volume 36, Issue 5
Displaying 1-12 of 12 articles from this issue
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Hiroharu HORIUCHI1979 Volume 36 Issue 5 Pages 287-292
Published: May 25, 1979
Released on J-STAGE: February 26, 2010
JOURNAL FREE ACCESSAqueous poly (vinyl alcohol) (I), partly esterified with formic, acetic, or propionic acid, was potentiometrically titrated with poly (methacrylic acid) (II). Plots of pH of the solution against mole fraction of the acid in the system show connected straight lines (or gentle curves) and the breaking points correspond to the characteristic compositions of components and/or their complex. At constant solute concentration the pH-curves for the mixture lead to conclude that, as a whole the ester group makes the I more basic and accessible to II, but it vitiates structural complementarity and accelerate the dissociation till the carboxyl group equals ester residue. In the regions covered by experiments, however, I and II form an equimolar polycomplex. Results from the conductance measurements support this. Relative viscosity pattern of I-II mixture will be a measure of aggregation in the system.View full abstractDownload PDF (1106K) -
Hiroyoshi KAMATANI, Shigeji KONAGAYA1979 Volume 36 Issue 5 Pages 293-298
Published: May 25, 1979
Released on J-STAGE: February 26, 2010
JOURNAL FREE ACCESSAs the first step to clarify the role of phosphorus compounds in the catalytic polycondensation of bis (2-hydroxyethyl) terephthalate, effect of phosphorus compounds on the activity of catalyst (Zn (II), Co (II), Mn (II)) was studied. When phosphoric acid was used, the polycondensation rate decreased linearly with increasing its molar ratio to the catalyst and the reaction practically did not proceed on addition of phosphoric acid of molar equivalent to the catalyst or more. The unfavorable effect of phenylphosphorus compounds decreased in the following order; (HO) 3PO>C6H5 (HO) 2PO> (C6H5) 2 (HO) PO> (C6H5) 3PO, the effect of triphenylphosphine oxide being negligible. By the addition of a trialkyl phosphate the activity of catalyst also decreased depending upon its alcohol component in the following order; (HO) 3PO> (CH3O) 3PO> (C2H5O) 3PO> (n-C4H9O) 3PO. It was made clear that this inhibitory effect of trialkyl phosphates is due to the complexation of the catalyst with phos-phoric acid which was formed in situ in the early stage of the polycondensation.View full abstractDownload PDF (992K) -
Syu WATARAI, Akira UMEHARA1979 Volume 36 Issue 5 Pages 299-303
Published: May 25, 1979
Released on J-STAGE: February 26, 2010
JOURNAL FREE ACCESSThe polymerization of 1, 3, 3-trimethy1-2-methyleneindoline (Fischer's base: FB (I)), prepared by Fischer's indole synthesis, was investigated. While the radical copolymerizations of FB (I) with ethyl acrylate or acrylonitrile in bulk using azobisisobutyronitrile as initiator gave alternating copolymers, no homopolymerization of FB (I) occurred under similar conditions. Comparison of the spectral data of FB (I) with those of the copolymers showed that the exo-methylene group in FB (I) was involved in the polymerization. The Q and e values of FB (I) were calculated to be 1.92 and -1.40, respectively. Under cationic polymerization conditions, FB (I) merely formed quaternary salts with protonic acids or Lewis acids due to the highly basic character of FB (I) and gave no polymeric products. Similar polymerization reactions of 5-substituted 1, 3, 3-trimethyl-2-methyleneindolines were also investigated.View full abstractDownload PDF (834K) -
Kazuo INOUE, Sadao HOSHINO1979 Volume 36 Issue 5 Pages 305-310
Published: May 25, 1979
Released on J-STAGE: February 26, 2010
JOURNAL FREE ACCESSThe effect of geometric isomers of 1, 3-cyclohexanebis (methylamine) (1, 3-CBMA) on the structure and properties of the polymers derived by the polycondensation of each diamine with adipic acid (6) was studied. The cis and trans isomers of the diacid salts of the diamine were obtained by recrystallizing cis/trans mixed salt from the solution and were polymerized. The polyamide with 97.4% cis residue was highly crystalline and melted at 253°C, while the polyamide with 93.3% trans residue was amorphous. The glass transition temperatures of these polymers were not so much different each other. They were 97 and 84°C for the polyamides with 97.4% cis and 93.3% trans residues, respectively. These results show that the chain conformation which is concerned with crystallinity and melting point is markedly influenced by the isomer, but the chain mobility which is related to glass transition temperature is not so much influenced.View full abstractDownload PDF (1550K) -
Hiroyoshi KAMATANI1979 Volume 36 Issue 5 Pages 311-315
Published: May 25, 1979
Released on J-STAGE: February 26, 2010
JOURNAL FREE ACCESSBis (2-hydroxyethyl) terephthalate is an important intermediate in the industrial poly (ethylene terephthalate) production. The reaction of terephthalic acid with ethylene oxide to form bis (2-hydroxyethyl) terephthalate was studied in the presence of Group V compounds (R3X; R=alkyl, phenyl, X=P, As, Sb) in organic solvents in order to clarify the catalytic action of these compounds. On the bases of the isolation of the intermediate and kinetic data, it was proved that the actual catalyst for the esterification was not R3X itself when X was phosphine or arsine but its quaternary salt of terephthalic acid (HO2C-C6H4-CO2 (-) X⊕ (R3) C2H4OH) formed from terephthalic acid, ethylene oxide, and R3X (X=P, As). On the other hand, when triphenylstibine was used as catalyst, quaternary stibonium terephthalate was not formed and hence the esterification reaction did not proceed. The rate of esterification of terephthalic acid with ethylene oxide decreased in the following order;
(n-C4H9) 3P> (C6H5) 3P>> (C6H5) 3As>> (n-C4H9) 3Sb, (C6H5) 3Sb.View full abstractDownload PDF (833K) -
Yasuo YUKI, Yasushi OSAKA, Akihiro YAMANE1979 Volume 36 Issue 5 Pages 317-320
Published: May 25, 1979
Released on J-STAGE: February 26, 2010
JOURNAL FREE ACCESSp-and m-Aminophenyldicyandiamides were prepared by the reduction of p- and m-nitrophenyldicy-andiamides using zinc powder and sodium chloride in water. p-and m-Aminophenyldicyandiamide hydrochlorides (p-and m-APDDHCl) were found from DSC measurement to change into poly (p- and m-phenylene biguanide hydrochloride) s by polyaddition reaction at 190-220°C for p-APDDHCl and at 150-180°C for m-APDDHCl. The poly (phenylene biguanide hydrochloride) s were also obtained by heating APDDHCI at 180°C or 200°C. The reduced viscosities of these polymers were 0.15-0.16 in dimethyl sulfoxide. Thermal properties of the polymers were examined.View full abstractDownload PDF (642K) -
Katsutoshi TANAKA, Hiromasa OGAWA, Yuko TANAKA1979 Volume 36 Issue 5 Pages 321-327
Published: May 25, 1979
Released on J-STAGE: February 26, 2010
JOURNAL FREE ACCESSDynamic mechanical properties of the blends of poly (vinyl chloride) (I) with 0-60 phr of ethoxymethylmelamine resin (II) partially thermo-set, have been examined. The dispersed state of II in I, was unchanged on heating. The modulus of the polyblends was higher, while the α-and β-peaks in the temperature-tan δ curves were lowered, than those of I itself. These facts suggest that the cured II acts as a filler. On the other hand, the glass transition temperature (Tg) of I, plasticized with eliminated molecules such as formaldehyde and ethanol, was lowered. These phenomena became more apparent as the II content increased. From these observations, the dynamic mechanical properties of the polyblends can be explained by using filled and plasticized matrix models, assuming the additive contribution of the both components.View full abstractDownload PDF (1333K) -
Takuji OKAYA, Kiyokazu IMAI1979 Volume 36 Issue 5 Pages 329-335
Published: May 25, 1979
Released on J-STAGE: February 26, 2010
JOURNAL FREE ACCESSDilute aqueous solution viscosities of poly (vinyl alcohols) (I) which were prepared by solution polymerization of vinyl acetate in higher primary alcohols were measured. Huggins' constant obtained from Schulz-Blaschke's equation, kS′ of conventional I is 0.4-0.5 depending slightly on the degree of polymerization, while kS′ of PVA prepared in cetyl and stearyl alcohols are higher than 0.5 and increase with the decrease of the degree of polymerization. In the case of I prepared in a lower alcohol than myristyl no abnormality in kS′ was observed. In dilute dimethyl sulfoxide solution of the polymers as well as in dilute acetone solution of re-acetylated polymers, no abnormality was also observed. Degree of polymerization of I derived from stearyl alcohol was calculated from the intrinsic viscosities of aqueous solution. It was larger by tens of % than the values calculated from the viscosities of dimethyl sulfoxide and acetone solutions. These results show the existence of intermolecular interaction or hydrophobic bond between the alkyl end groups of I in aqueous solution which are introduced by chain-transfer reaction during the polymerization.View full abstractDownload PDF (1126K) -
Tomoyuki KASEMURA, Fumio UZI, Takasi KONDO, Toshio HATA1979 Volume 36 Issue 5 Pages 337-342
Published: May 25, 1979
Released on J-STAGE: February 26, 2010
JOURNAL FREE ACCESSSurface tensions (γ) of poly (vinyl alkylate) s with side chains of various lengths from C2 to C16 were measured by the sessile bubble method at various temperatures. Surface tension, surface energy and surface entropy decrease with the increase of the side chain length. After reaching the minimum value at C8, they increase again. The components of surface tension due to the dispersion force (γd) and the polar force (γp) were calculated by Fowkes' equation from interfacial tension data. Both γd and γp decrease rapidly with the length of side chain and γd approaches γ and γp nearly zero at PV-C6. MacLeod's exponent (β) decreases with side chain length from 3.9 to 3.2. The relation of dln γ/dT=αβ, where α is the thermal expansion coefficient, was verified experimentally.View full abstractDownload PDF (1015K) -
Seizo MASUDA, Tadatoshi OTA1979 Volume 36 Issue 5 Pages 343-346
Published: May 25, 1979
Released on J-STAGE: February 26, 2010
JOURNAL FREE ACCESSα-Cyanovinyl acetate (α-CN·VAc) is polymerized anionically at 70°C in the presence of pyridine, a weak base, although the presence of strong base such as butyllithium leads to decomposition of the monomer. The anionic polymerization accompanies radical polymerization at a relatively high temperature. Pyridine in concentration up to 0.12 mol/l works inhibitory for the radical polymerization of α-CN·VAc, while it serves efficiently as anionic catalyst in the presence of p-benzoquinone. The rate of the anionic polymerization is directly proportional to the concentration of pyridine. In the anionic bulk-copolymerization of α-CN·VAc (M1) and styrene (M2), pyridine-benzoquinone catalyst gives r1=10.0 and r2=0.01.View full abstractDownload PDF (499K) -
Noriyuki KAMEDA, Emiko ISHII1979 Volume 36 Issue 5 Pages 347-349
Published: May 25, 1979
Released on J-STAGE: February 26, 2010
JOURNAL FREE ACCESSThe solvent effect on the polymerization of methyl methacrylate (MMA) initiated by hydrido-carbonyltris (triphenylphosphine) rhodium (I) -carbon tetrachloride was studied. The polymerization rate was found to decrease in the following order; DMSO>DMF>THF>benzene. When DMSO was used as a solvent, the concentration of DMSO had a great influence on the polymer yield and the composition curve of the copolymerization of styrene with MMA agreed with that of the ordinary radical polymerization.View full abstractDownload PDF (442K) -
Hajime MIYAMA, Noriho HARUMIYA1979 Volume 36 Issue 5 Pages 351-353
Published: May 25, 1979
Released on J-STAGE: February 26, 2010
JOURNAL FREE ACCESSRate of photopolymerization of acrylonitrile in dimethylsulfoxide initiated by bromoform was measured at 25, 35, and 45°C. As a result, the rate expression Rp=6.26 exp {(-2.6kcal/RT)} √Iab [M] was obtained, where Rp, Iab, and [M] were rate (mol·l-1·s-1), absorbed light intensity (E·l-1·s-1) and monomer concentration (mol·l-1).View full abstractDownload PDF (380K)
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