Kobunshi Kagaku
Online ISSN : 1884-8079
Print ISSN : 0023-2556
ISSN-L : 0023-2556
Volume 22, Issue 247
Displaying 1-14 of 14 articles from this issue
  • I. Non-Newtonian Flow
    Takuro Hayahara, Seiji Takao
    1965 Volume 22 Issue 247 Pages 673-678
    Published: November 25, 1965
    Released on J-STAGE: October 14, 2010
    JOURNAL FREE ACCESS
    The viscosity of concentrated solutions of acrylonitrile copolymer having different molecular weight in different polymer concentration was measured under high shear stresses.
    Log-log plots of viscosity against molecular weight indicate straight lines at a series of constant shear stress with slopes that decrease from 2.67 towards 1.40 with increasing shear.Log-log plots of viscosity against polymer concentration also indicate straight lines at a series of constant shear rate.
    If these plots are extrapolated to the range of lower molecular weight or lower polymer concentration, it was found that these plots converged to a point. The point found experimentally is considered to be an entanglement transition point which was obtained from the measurements of zero-shear viscosity, as functions of molecular weights and polymer concentrations.
    At the entanglement transition region, we have observed experimentally the following relationship between critical molecular weight and critical polymer concentration,
    M0.54C=K (constant)
    where K is little affected by temperature.
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  • I. Physical Properties of the Copolymer
    Nobuo Ueda
    1965 Volume 22 Issue 247 Pages 679-685
    Published: November 25, 1965
    Released on J-STAGE: February 20, 2012
    JOURNAL FREE ACCESS
    Studies were made on the physical properties of ethylene glycol terephthalate/diethylene glycol terephthalate [PET/(DEG) T] copolymer over the entire range of copolymerization composition.
    (a) The copolymer having the mole fraction of (DEG) T greater than 0.5 shows rubber-like elasticity. Although P (DEG) T has heretofore been obtained only in crystalline state, it crystallized under severe conditions (60°C, 10hr, in solvent). The X-ray diffraction patterns indicate the formation of a new crystalline polymer different from PET.
    (b) The melting point Tm of the crystalline PET/(DEG) T copolymer conforms of Flory's equation. The heat offusion is approximately 2793 cal per ET unit.
    (c) The glass transition point of PET/(DEG) T is given by Gordon-Taylor's equation:
    _??_
    where w2 is the molar fraction of PET, K is a constant equal to 0.685.
    (d) The relation between the specific volume of the amorphous copolymer and its composition shows that the free volume increases with the mol fraction of (DEG) T.
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  • II. Determination of Copolymer Composition by High Resolution NMR Spectroscopy
    Toyotaro Harada, Nobuo Ueda
    1965 Volume 22 Issue 247 Pages 685-690
    Published: November 25, 1965
    Released on J-STAGE: October 14, 2010
    JOURNAL FREE ACCESS
    The copolymer composition of ethylene glycol terephthalate/diethylene glycol terephthalate [PET/(DEG) T] was determined by high resolution NMR spectra of the copolymer in o-chlorophenol.
    1) The composition of PET/(DEG) T can be determined from the intensity of a signal at 3.8ppm relative to that at 4.5ppm, both being assignable to two sorts of methylene protons.
    2) The sequence of monomer units is discussed on the basis of the phenylene peaks of PET/(DEG) T by Bovey and coworker's method. The distribution of monomer-unit sequences deviates from that expected from the equal reactivities of the functional groups.
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  • Kenji Kamide, Yoshihiko Inamoto
    1965 Volume 22 Issue 247 Pages 691-695
    Published: November 25, 1965
    Released on J-STAGE: October 14, 2010
    JOURNAL FREE ACCESS
    In order to evaluate the contribution of draining effect of polymer chain to thesolution properties and to determine the dependence of the configuration on the solvents, intrinsic viscosity-molecular weight relationships (Mark-Houwink equations) for various solutions of amylose were analyzed on the basis of Kamide and et al's treatment (this journal, 20, 512 (1963); 21, 682 (1964)). The solvents used were classified into two groups;(a) Dimethylformamide (DMSO)-water and DMSO-M/2 KCl, (b) DMSO, DMSO-methanol, DMSO-acetone, water and formamide. In the case of ethylenediamide (EDA) and EDA-M/2 KCl the solutions behave differently from groups (a) and (b), owing to their strong affinity for moisture. Flory constants K obtained were 6.2×10-4 and 8.0×10-4 for groups (a) and (b), respectively. The characteristics of group (a) may be explained by the specific interaction of the polymeric chain molecules with the complex, DMSO ……2H2O, formed in the solutions. It became clear that the draining effect can be almost completely neglected in the solution of amylose.
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  • I. Hydrolysis of Linear Aliphatic Monoesters with Polystyrene Sulfonic Acid
    Ichiro Sakurada, Yasuyoshi Sakaguchi, Tomoyoshi Ono, Toshio Ueda
    1965 Volume 22 Issue 247 Pages 696-701
    Published: November 25, 1965
    Released on J-STAGE: October 14, 2010
    JOURNAL FREE ACCESS
    Hydrolysis of linear aliphatic monoesters was carried out in aqueous solutions with hydrochloric acid or polystyrene sulfonic acids (PS-S) of various degrees of sulfonation as catalysts and the rates of hydrolysis were compared. As far as the comparison was done under the equivalent acid concentrations the catalytic activities of PS-S were generally greater than that of HCl, and increased with the decrease of their sulfonation degrees and the solubility of the esters in water. Rise of reaction temperature and an addition of acetone to the reaction mixture reduced considerably the effectiveness of PS-S. On the basis of these results, it seems that the hydrogen ion is concentrated in the neigbourhood of polymer molecules and the hydrophobic interaction between PS-S and the ester increases the local concentration of the ester in the neigbourhood of polymer molecules.
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  • II. Hydrolysis of Various Aliphatic Esters with Polystyrene Sulfonic Acid
    Ichiro Sakurada, Tomoyoshi Ono, Toshio Ueda, Yasuyoshi Sakaguchi
    1965 Volume 22 Issue 247 Pages 701-705
    Published: November 25, 1965
    Released on J-STAGE: October 14, 2010
    JOURNAL FREE ACCESS
    The hydrolysis of branched aliphatic esters, acetylated polyhydric alcohols and diesters of dibasic acids was carried out in aqueous solutions with polystyrene sulfonic acids (PS-S) of various degrees of sulfonation as catalysts. In the hydrolysis of branched aliphatic esters the effects of branching of alcohol component in butyl acetates and of acid component in methyl valerates were studied, and it was found that in both cases the branching of the esters reduced the catalytic efficiency of PS-S. Acetylated polyhydric alcohols such as ethylene acetate, triacetin, diacetin, monoacetin and acetylmannitol, and diesters of dibasic acids such as methyl fumarate and methyl maleate were used. In all cases, PS-S was a more active catalyst than hydrochloric acid, but the activity was only slightly affected by that the esters were polyvalent.
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  • III. Hydrolysis of Aliphatic Esters with Various Polymer Sulfonic Acids
    Ichiro Sakurada, Yasuyoshi Sakaguchi, Tomoyoshi Ono, Toshio Ueda
    1965 Volume 22 Issue 247 Pages 706-711
    Published: November 25, 1965
    Released on J-STAGE: October 14, 2010
    JOURNAL FREE ACCESS
    The hydrolysis of aliphatic esters with various polymer sulfonic acids was carried out. In aqueous solutions vinyl-sulfonic acid-styrene copolymer was a more active catalyst than hydrochloric acid, and the activity was nearly as great as that of polystyrene sulfonic acid. Polyvinylbutyral sulfonic acid and vinylsulfonic acid-vinylalcohol copolymer, however, showed no greater catalytic activity than hydrochloric acid. The catalytic activity of polystyrene sulfonic acids depended on their preparation methods. Partial neutralization of polystyrene sulfonic acids with quaternary ammonium hydroxides reduced the catalytic activity of theremaining hydrogen ions. In aqueous acetone such a difference between the activities of polymer sulfonic acids was not found. Some discussions were given for the results.
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  • IV. Hydrolysis of Aromatic Esters with Polymer Sulfonic Acids
    Ichiro Sakurada, Tomoyoshi Ono, Yasuyoshi Sakaguchi
    1965 Volume 22 Issue 247 Pages 711-716
    Published: November 25, 1965
    Released on J-STAGE: October 14, 2010
    JOURNAL FREE ACCESS
    The hydrolysis of aromatic esters with various polymer sulfonic acids was carried out. For the hydrolysis of methyl benzoate in water, polystyrenesulfonic acid (PS-S) was a more effec-tive catalyst than hydrochloric acid, but an addition of acetone reduced the catalytic efficiency. The catalytic effect of polyvinylacetal sulfonic acid, polyvinylsulfonic acid and vinylsulfonic acid vinylalcohol copolymer were nearly the same as that of hydrochloric acid. Also for the hydrolysis of methyl o-and p-hydroxybenzoates in water PS-S was more effective than hydrochloric acid; these two esters showed somewhat different behavior by the hydrolysis. In aqueous acetone the substituents such as p-and o-hydroxy, p-nitro and p-chloro showed little difference in the catalytic effect of polymer sulfonic acids. Partial neutralization of PS-S with quaternary ammonium hydroxides reduced the catalytic effect of the remaining free sulfonic acid groups for the hydrolysis of the benzoates. Hydrolysis of some other esters with ring structure was also studied.
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  • VI. Polymerization of Aldehydes with Alkaline-Earth-Metal Ketyls
    Hiroshi Takida, Ken Noro
    1965 Volume 22 Issue 247 Pages 717-724
    Published: November 25, 1965
    Released on J-STAGE: October 14, 2010
    JOURNAL FREE ACCESS
    Polymerization of aldehydes at low temperatures with alkaline-earth-metal ketyls as catalyst was studied. It was observed that crystalline polymers were obtained in high polymer yield with these catalysts. Magnesium, barium and calcium were used as alkaline-earth-metal and benzophenone, Michler's ketone and benzyl were used as aromatic ketones. At the lower temperature of the polymerization, was higher value the crystallinity of the obtained polymer. It was possible to obtain block copolymers of acetaldehyde by using living polymers which obtained by polymerization of vinyl monomers with these complexes as catalyst. Normal and iso-butyraldehyde and chloral could be polymerized also with these complexes as catalyst.
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  • VII. Polymerization of Aldehydes with Alkali-Metal Ketyls
    Hiroshi Takida, Ken Noro
    1965 Volume 22 Issue 247 Pages 724-733
    Published: November 25, 1965
    Released on J-STAGE: October 14, 2010
    JOURNAL FREE ACCESS
    Polymerization of aldehydes with alkali-metal ketyls as catalyst was studied. Lithium, sodium and potassium were used as alkali metals and benzophenone, Michler's ketone and benzyl were used as ketones. High polymer yield was obtained when the polymerization was carried out at -78°C with lithium complexes. When sodium complex was used as catalyst, polymer yield at-78°C was lower than that at-100°C. Only low polymer yield was obtained as potassium complex was used as catalyst. Block copolymerization of acetaldehyde was attempted by using living polymers which obtained by polymerization of vinyl momomers with these complexes as catalyst. It was possible to polymerize n-, iso-butyraldehyde and chloral with these complexes. In the polymerization of aldehyde with these complexes, it is considered from the infrared spectra of low molecular weight polymer that alcohlate anion of metal ketyl participates in initiation of the polymerization. Effects of metallic and organic components of complexes on the polymerization of acetaldehyde were also discussed.
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  • I. Action of Metallic Salts in Polyester Synthesis
    Akira Suzuki, Nobumasa Hojo
    1965 Volume 22 Issue 247 Pages 734-738
    Published: November 25, 1965
    Released on J-STAGE: October 14, 2010
    JOURNAL FREE ACCESS
    The role of metallic salts in polyester synthesis were discussed. If the reaction products from metallic salts and the initial components of polyester act as an accelerator, then reaction will be promoted, when the metallic salts are replaced by the reaction products. The reaction product (A) of ethyleneglycol (EG) and Zn was prepared from EG and zinc acetate, and that (B) of dimethylterephthalate (DMT) and Zn was from DMT and zinc acetate in dimethylformamide solution. As a reaction accelerator, zinc acetate or the above reaction product is added to the mixture of the definite composition of DMT, EG and glycerine. All synthesis tests were done under the same condition. During the condensation, the changes of OH value, acid value and viscosity with time were measured. The effects of zinc acetate, A and B on OH value, acid value and viscosity were compared, under the same concentration of Zn. With regard to accelerating action, A is comparable to zinc acetate and is more effective than B.
    The metallic salts are expected to have an accelerating property for polyester synthesis, after these react with EG and DMT.
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  • Shunsuke Murahashi, Shun-ichi Nozakura, Yasuharu Imai
    1965 Volume 22 Issue 247 Pages 739-745
    Published: November 25, 1965
    Released on J-STAGE: December 22, 2010
    JOURNAL FREE ACCESS
    In order to obtain further information on the reactivities of cis- and trans-isomers of 1, 2-disubstituted ethylenes of the nonconjugated type, the copolymerizations of cis- and trans-dimethoxyethylenes (DME) and p-dioxene (PD) with maleic anhydride (MAn) or maleimide (MIm) were carried out. Since DME and PD gave 1: 1 copolymers with MAn, the reactivities were compared by the overall rate:
    cis-DME≥trans-DME≥PD
    The reactivities with MIm radical were compared by the determination of the monomer reactivity ratios as follows (MIm=M1).
    trans-DME≥cis-DME≥PD
    (1/r1=trans-DME 5.2, cis-DME 4.5, PD 0.78)
    The data indicated that there was no significant difference in reactivities between cis- and trans-isomers of DME and that DMEs were about 6 times as reactive as PD. These results were rationalized by considering the steric structure of the monomers.
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  • Akitomo Gotoh, Natsuki Kanoh, Toshinobu Higashimura
    1965 Volume 22 Issue 247 Pages 746-751
    Published: November 25, 1965
    Released on J-STAGE: December 22, 2010
    JOURNAL FREE ACCESS
    p-Aminobenzyl cyanide hydrochloride afforded a polyamidine hydrochloride of structure (I) by heating it at 200-230°C. Viscosity (ηsp/C) of the polymer increased with increase of
    _??_
    conversion and was up to 0.2 measured at a concentration of 2.0 g/100 ml of formic acid at 30°C. The polymer (I) was soluble in water and formic acid, but polymer obtained by dehydrochlorination of (I) with aqueous ammonia was insoluble in water. An attempt to polymerize p-aminobenzyl cyanide with Friedel-Crafts catalyst such as aluminum trichloride was unsuccessful to obtain a linear, well-defined polyamidine.
    Aminoacetonitrile hydrochloride did not produce a polymer under the condition tried.
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  • Tsutomu Kagiya, Sueo Machi, Masao Gotoda, Ken-ichi Fukui
    1965 Volume 22 Issue 247 Pages 752-760
    Published: November 25, 1965
    Released on J-STAGE: October 14, 2010
    JOURNAL FREE ACCESS
    In the polymerization which is characterized by the increase of polymerization rate and growth of molecular weight with reaction time or conversion, the hypothesis of stationarystate is not realized. In this paper, a kinetical consideration on the basis of nonstationarystate is presented for the polymerization in which the rate of initiation is smaller than that of propagation. The quantitative relation between reaction condition and both molecular weight of polymer and rate of polymerization are proposed. Several typical examples of no termination; polymerization of ethylene and acrylonitrile with initiator, ethylene and vinyl chloride by γ-radiation, ethylene and propylene with complex catalyst were discussed and above theoretical relation is shown to be well applied to those kinetical data.
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