Sen'i Gakkaishi
Online ISSN : 1884-2259
Print ISSN : 0037-9875
Volume 20, Issue 5
Displaying 1-6 of 6 articles from this issue
  • (VI) DISCUSSION ON THE SIGNIFICANCE OF ZINC ION IN THE SPINNING BATH. (VII) THE EFFECTS OF MODIFIERS ON THE FIBER FORMATION OF VISCOSE RAYON (VIII) THE DISCUSSION ON THE FORMATION OF COLLOIDAL
    Eiichi Murakami
    1964 Volume 20 Issue 5 Pages 289-305
    Published: May 10, 1964
    Released on J-STAGE: November 28, 2008
    JOURNAL FREE ACCESS
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  • Kan Shirakashi, Kinzo Ishikawa, Keizo Miyasaka
    1964 Volume 20 Issue 5 Pages 306-310
    Published: May 10, 1964
    Released on J-STAGE: November 28, 2008
    JOURNAL FREE ACCESS
    The Flory's theory on swelling of network high polymer was applied on the network graft polymer.
    The model used to derive the equation of swelling was constructed under the following assumptions:
    1) Backbone polymer chains are crosslinked and branch polymer chains are deposited in the network of backbone polymer.
    2) Heat of mixing for graft polymer and solvent is assumed to be of van Laar type.
    3) Graft polymer being swollen, network chains are deformed entropicaly.
    The derived equation is as follows:
    where χ1: parameter expressing the energy of interaction between solvent and graft polymer
    P: moles of branch chains
    υe: moles of chains between the network junctions in the backbone polymer network
    f: number of backbone chains crosslinked at one crosslinkage
    υp: volume fraction of graft-polymer at swollen state
    υν0: volume fraction of backbone polymer chains at non-swollen state
    V0: volume of graft polymer at non-swollen state
    V1: mole volume of solvent
    M: primary molecular weight of backbone polymer
    Mc: molecular weight per cross-linked unit of backbone polymer
    ρν: density of backbone polymer
    These equations are modified further for crystalline graft-polymer.
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  • Kimihiro Suzuki, Iichiro Kido, Hiroshi Takeuchi, Shigemasa Nakazawa, T ...
    1964 Volume 20 Issue 5 Pages 311-318
    Published: May 10, 1964
    Released on J-STAGE: November 28, 2008
    JOURNAL FREE ACCESS
    Based on our experience of the vapour phase acetylation of cellulose, the vapour phase grafting of methyl acrylate, ethyl acrylate, methyl methacrylate and acrylonitrile onto viscose rayon pretreated by cerium ammonium nitrate solution were studied and the influence of the initiator and nitric acid concentration in the pretreating solution, atmospheric pressure in the reaction vessel, and reaction temperature upon the grafting were investigated. Some mechanical properties of the grafted rayon were measured. The results obtained are as follows:
    (1) For e. g. AN grafting, about 150% retention of the pretreating solution by the rayon is most favourable.
    (2) MA or EA grafting is the first order reaction, MMA the sigmoid, and AN the fibrous reaction controlled by diffusion.
    (3) Ultimate graft amount of each monomer shows the maximum in relation to the initiator and nitric acid concentration in the pretreating solution.
    (4) Ultimate graft efficiency of AN or MMA is about 90%, but that of MA or EA decreases linearly with the initiator concentration.
    (5) Ultimate graft amount of each monomer decreases with the increase of carbonyl content of the rayon when the initiator concentration is increased.
    (6) DP of MMA graft polymer increases nearly parallel to the increase in the amount of graft with reaction time. The minimum of DP curve of ultimate graft polymer with respect to the initiator or nitric acid concentration, corresponds nearly to the maximum of the related graft amount curve.
    (7) The apparent activation energies obtained are MA6.7, EA8.5, MMA8.2, and AN 10.1 kcal/mol.
    (8) Atmosphere in the reaction vessel controlls the monomer vapour diffusion by the pressure variation and retards the grafting by oxygen in air. If air is replaced by nitrogen, graft amount of MA or EA increases several folds, but that of MMA or AN does not.
    (9) The breaking load of the grafted rayon is almost constant, the extension increases slightly, the initial modulus of MA or EA grafted decreases slightly, that of MMA or AN grafted increases slightly with graft amount.
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  • Yasuji Nakahara
    1964 Volume 20 Issue 5 Pages 319-323
    Published: May 10, 1964
    Released on J-STAGE: November 28, 2008
    JOURNAL FREE ACCESS
    Dyeing properties of cuprammonium fiber (BF) graftpolymerized with glycidyl methacrylate (GMA) are studied, especially for substantive dye Congo Red and basic dye Magenta. These two dyes contain amino groups in their molecules, which can react with epoxide of GMA. Magenta stains so fast BF-GMA as reactive dyeing, but Congo Red stains the fiber not so fast as reactive dyeing without pyridine catalyst in the dye bath. The adsorbed Magenta on BF-GMA can not be extracted by normal organic solvents (o-chlorophenol, dimethylformamide etc.), while the adsorbed Congo Red on BF-GMA is extracted easily by these solvents.
    The dyeing properties of BF-GMA for Congo Red in absence of catalyst are similar to that of normal substantive dyes; the higher the dyeing temperature the higher becomes the dyeing velocity and the lower maximum txhausion of dye. By addition of pyridine as catalyst in the dye bath, dyeing temperature affects only the dyeing velocity, and the maximum exhaution of dye showes the same value at each temperature in equilibrium. By adding the catalyst The velocity of exhation of dye Congo Red by BF-GMA apparently takes the second order reaction between dye molecules and epoxides on the fiber. The activation energy of the reaction is large enough (ca. 20 kcal.), to be concidered as a chemical reaction. What is interesting is, that Magenta adsorbed on BF-GMA shows quite different hue from that on wool, acrylic fiber or cuprammonium fiber graftpolymerized with acrylonitrile (BF-AN), all dyed under the same condition. Dye of this hue (just like that of Crystal Violet) is synthetized by reaction of Magenta and by reaction of Magenta and GMA in ethyl alcohol at boiling point adding hydroquinone as a inhibitor for polymerization reaction. We have named this new dye “Nobeoka Violet”, which have the maximum absorbtion at 610mμ in aqeous solution.
    The dyed pieces of BF-GMA with Magenta and BF-AN with Nobeoka Violet are scarcely distin-guishabe from each other by the hue. It is assumed, that Nobeoka Violet is synthetized on fiber in dyeing of BF-GMA by Magenta.
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  • (XI) THE INTERACTION BETWEEN AMINOANTHRAQUINONE TYPE DISPERSE DYES AND ALCOHOLS BY PAPERCHROMATOGRAPHY
    Yoshio Suda, Hideo Uzigawa
    1964 Volume 20 Issue 5 Pages 324-330
    Published: May 10, 1964
    Released on J-STAGE: November 28, 2008
    JOURNAL FREE ACCESS
    It was prevlously reported by us2), 3), 4) thatα-CH…X-Dye type hydrogen bonding made an important contribution to the interaction between disperse dyes and ester type fibres.
    In oraer to obtain other suggestions, the interaction between alcohols and disperse dyes is discussed in this paper, using paperchromatography, and noted with the results as follows:
    1) In similar manner to esters and amines, there exists the correlation between Rf value and alcohol concentration [A].
    Change of free energy (-ΔF) of interaction may be calculated from the estimated K.
    2) There is a certain correlation between (-ΔF) and carbon number (C) of alcohol, when the data are plotted on the ordinate and abscisa, respectively,
    therefor (-ΔF)=α•C+b ………(1)
    where a; apositive constant and b; a constant.
    3) The slope a of (1) is related to the molecular weight of dye (Dw) by the equation a=ADw+B ………(2)
    where A; a positive constant and B; a constant.
    4) The results 2) and 3) can not be explained by proton donating or accepting mechanism alone and suggest that an important contribution can be ascribed to van der Waals force as the interaction force between alcohol and dyes.
    But, this does not contradict the co-existence of other forces.
    5) Hence, it is supposed that van der Waals force makes a good part of contribution to disperse dyeing, too.
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  • Haruo Sanuki
    1964 Volume 20 Issue 5 Pages 331-337
    Published: May 10, 1964
    Released on J-STAGE: November 28, 2008
    JOURNAL FREE ACCESS
    By the flowing-out method-a single operation which does not press positively-the author has measured, as a fundamental analysis with 14 kinds of solvent and greasy wool, the required time tf (sec) for the first flowing-out, the quantity Qf (cc/sec) of flowing-out liquor per unit time the solvent ratio αf, the quantity Yf (g) of solid yolk removed, the residual suint value sRf (%), the residual grease value gRf (%) and the residual yolk value yRf (%)-and observed how far they vary with the kind of solvents. The wool samples were Merino-type, greasy, grade 64' S, with a yolk content of 25.28±1.26% (suint 7.72±0.36%, grease 17.56±0.90%, shown by a 95% degree of confidence).
    The author concludes in this article that:
    (1) Each residual yolk value of sample wool assembly treated by Acetone, Methyl Ethyl Ketone and Anon was extremely large.
    (2) Synthetic solvents are synthetically more suitable than petroleum solvents for the flowing-out method.
    (3) The mechanical removing action for yolk acts effectively in the flowing-out method.
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