巻号一覧
23 巻, 12 号
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第4報 単斜晶結晶の三主屈折率について高原 弘和, 河合 弘迪, 山田 哲三1967 年 23 巻 12 号 p. 571-577
発行日: 1967/12/10
公開日: 2008/11/28
ジャーナル フリーThe principal refractive indices of monoclinic crystal of isotactic polypropylene were evaluated by simulaneous measurements of x-ray diffraction, infrared dichroism and birefringence.
The _??_o_??_al birefringence of crystalline polymer can be represented as follows; on the basis of simple additivity of the crystalline and non-crystalline contributions. In uniaxially oriented system, the cystalline birefringence, Δc can be further represented in terms of the orientation factors and refractive indices of three orthogonal principal axes of oriented crystallites as follows: where na′, nb and nc are the refractive indices along the orthogonal axes, a′, b- and c-axis, respectively, and fα and fβ are the orientation factors for a′- and b-axis with respect to the stretching axis of bulk polymer.
When the orientation factor of non-crystalline chain segments can be directly determined from a measurable quantity, such as infrared dichroism, the non-crystalline birefringence, Δa can be calcuated by using proper value of intrinsic birefringence of the segment; the crystalline birefringence can be separated from the total birefringence. From the crystalline birefringence thus separated and the oriention factors of crystal a′- and b-axis, the values of (na′-nc) and (nb-nc) can be evaluated.
Along the above experimental procedure using well-annealed and relatively low-stretched isotactic polypropylene films, for which the crystal a′-and b-axis showed negative orientation of different degree from each other i.e., fα′_??_fβ the fowllowing conclusings were reached:
1) The 1155cm-1 band in infrard spectrum was found to be parallel dichroic non-crystalline band and the the angle between the non-crystalline chain segment axis and the transition moment of the band to be 42.8°.
2) Among the literatured values of intrinsic birefringence of monoclinic crystallite and noncrystalline chain segment, the values given by Samuels as Δ0c:33.1×10-3 and Δ0σ:46.8×10-3 seemed to be the most proper.
3) The principal refractive indices of monoclinic isotactic polypropylene crystal along the a′-, b- and c-axis were found as follows.
na′=1.5067, nb=1.5070 nc=1.5419.抄録全体を表示PDF形式でダウンロード (486K) -
上出 健二, 望月 サカエ, 池田 佐喜男1967 年 23 巻 12 号 p. 578-588
発行日: 1967/12/10
公開日: 2008/11/28
ジャーナル フリーFractions, blends and whole polymers from three kinds of isotactic polypropylene were melt spun at spinning draft 50 (diameter and length of straight die used, 0.45 and 0.5mm, respectively, the rate of output 0.765cc/min., winding velocity 250m/min), at the optimum spinning temperature. The mechanical properties were measured on the undrawn filaments having the same crystal form (monoclinic) and the same degrees of crystallinity and orientation. The results obtained are summerized as follows:
(1) The optimum spinning temperature is a function of viscosity-average molecular weight only.
(2) Since molecular weight degradation is avoidable during melt spinning process, the filament melt spun from fraction has rather wide distribution (where, _??_, weightaverage molecular weight, _??_, number-average molecular weight).
(3) Stress-strain relations vary widely with molecular weight of filaments.
(4) Yield stress is remarkably influenced by the molecular weight retension during melt spinning process. Compared with the retention of the same degree yield stress increases with the increase of molecular weight.
(5) Yield extension attains amximum at, where, _??_is viscosity-average molecular weight.
(6) Both breaking strength and breaking energy increase with increasing molecular weight, depending on a polymer type.
(7) Breaking extension reaches maximum at independent of a polymer type and molecular weight distribution. This behabior is similar to molecular weight dependence of stretchability of filaments.
(8) Elastic recovery at 10% extension reaches maximum at.
(9) Relaxation modulus decreases in inverse proportion to log t (where, t time) and attains maximum at _??_, compared with the same t.
(10) Abrasion strength increases with molecular weight.抄録全体を表示PDF形式でダウンロード (738K) -
第3報 ポリエチレン1, 2-ジ(m-メチルフェノキシ)エタン-p, p′-ジカルボキシレート山本 吉威, 三軒 齊, 今村 力造1967 年 23 巻 12 号 p. 589-594
発行日: 1967/12/10
公開日: 2008/11/28
ジャーナル フリー1, 2-di (m-methylphenoxy) ethane-p, p′-dicarboxylic acid (A) was derived from m-cresol by the similar procedure as 1, 2-di (o-methylphenoxy) ethane-p, p′-dicarboxylic acid (B) described in the previous paper. The former is a new compound as well as the latter. The polyether-ester (I) having the following chemical formura was then prepared by the polycondensation of the dimethylester of (A) with ethyleneglycol.
The effects of the position of CH3 group in the benzene ring of (I) on the physical properties and fiber-forming property were studied in comparison with those of the CH3 group in poly (ethylene-1, 2-di (o-methylphenoxy) ethane-p, p′-dicarboxylate) (II) reported in the previous paper.
(II) crystallizes from the melt on cooling, while (I) solidifies in glassy state without crystallization. The amorphous (I) crystallizes by immersing it in methanol at 50°C for about 5 hrs. It's melting point is 157°C_??_162°C, while that of (II) is 238°C_??_240°C (measured by the hot plate method). The melting point ratio (absolute temperature) of (I) to (II) is equal to that of dimethylester of (A) to (B). The glass transition temperature of (I) measured by a differential thermal analysis is 52°C. It is also lower than that of (II); 72°C.
The lowering of crystallinity, the melting point and glass transition temperature of (I) is due to the inhibited co-planarity of the ethylene-ester with benzene ring by a steric effect of the methyl group on a carbonyl group.
However, (I) can be melt-spun and the tensile strength of drawn fiber of (I) is a little inferior to that of (II) but is still within a range of practical use. The melt-spun fiber of (I) is drawn more readily as compared with (II).
The fiber period for (I) is calculated as 36.2 A from X-ray diffraction patterns of fiber (I) drawn into 7 times length and annealed at 120°C for half hour. The value is about double of that of (II); 18.5 A as well as that of the basic polymer having no methyl group; 18.7 A. This means that the conformation of molecular chain is not planar at carbonyl-benzene bond and the twisted state returns back over two chemical repeating units.
In conclusion, it may be interpreted that the differences in above-mentioned properties between (I) and (II) arise from the ortho effect of methyl group and carboxylate group in (I).抄録全体を表示PDF形式でダウンロード (944K) -
新井 幸三, 根岸 道治1967 年 23 巻 12 号 p. 595-601
発行日: 1967/12/10
公開日: 2008/11/28
ジャーナル フリーThe kinetics of graft copolymerization of methyl methacrylate onto silk fibroin or wool keratin fibers in aqueous LiBr-K2S2O8 redox system was studied.
It was found that the grafting occurred by the radicalotoropy to the active centers of silk fibroin or wool keratin fibers from the radicals formed by the redox system, not by the chain transfer mechanism. From the experimental results at different temperatures, the activation energies for reaction steps were calculated. From these results, the thiol groups on wool keratin are considered to be predominantly in the center of grafting, but it is suggested that the grafting site of silk fibroin fibers differs from that of wool keratin fibers.抄録全体を表示PDF形式でダウンロード (491K) -
第11報 アミランへのアゾ系酸性染料の拡散清水 融, 大矢 精治, 伊藤 和夫, 久米田 寛1967 年 23 巻 12 号 p. 602-609
発行日: 1967/12/10
公開日: 2008/11/28
ジャーナル フリーThe rates of dyeing were measured on 14 acid azo dyes on Amilan (nylon 6) in the infinite dyebath buffered in the range of pH 2-7, at the dye concentration between 1×10-5 and 1×10-8 eq/l, and at 59°C. The apparent diffustion coefficients D were obtained by using Hill's equation.
D, in each dye, varies with the equilibrium uptake of dye M∞. The decrease in D with the increased number of sulfonic acid groups and the enlargement of volume in the molecule (or affinity) of dye is observed, if θ=M∞/S <1 (S is saturation value), when compared with the same value of M∞ or θ. Since the variation in D with θ may be anomalous if θ>1, a comparison of the dyeing rates of different dyes, obtained at a constant concentration of dye and pH in the bath, does not give a regular relation between D and the molecular structure of dye.
In the range of pH investigated, the amino azo dyes with high pk-value produce ampho-ions in great quantities, leading to the significant irregularity in D-M∞ curves.抄録全体を表示PDF形式でダウンロード (493K) -
第1報 繊維の品種による相違(その1)佐貫 治夫, 松原 昭1967 年 23 巻 12 号 p. 610-616
発行日: 1967/12/10
公開日: 2008/11/28
ジャーナル フリーIn recent years, much attention has been directed towards burning accidents involving apparel fabrics, quilting wads, interior cloth and fabrics for fire fighting, industry, etc. The flame-retardant finish must be applied to these textile goods. The detailed investigation of burning behavior of various kinds of fiber assemblies is prerequisite to the effective flame-retardant finish. It is presumed that the burning behavior of a fiber assembly differs exceedingly with a kind of fiber. In this study, the measurements were made by the new test method to see how much the burning rate differs of with the assembly of seven kinds of flammable fibre at windless condition depending on the fiber.
Each sample of the chemical fiber was scoured with aqueous solution of non-ionic detergent, and then repeatedly rinsed with distilled water, finally being dried and conditioned. Raw cotton was scoured with alkali solution of high temperature. The artificial assemblies of approximately the same constructive density were made from these various kinds of scoured loose fiber for the to be experiment. The different degrees of porosities (degrees of opening) of fiber assemblies were made available by stuffing the specified quantity (3 grams in absolute dry weight) of each sample fiber into the cylindrical containers (10cm in height) which were made of stainless steel wire nettting with various capacities. The column of sample fibre assembly was made hung on the arm of strain-gauge in a burning box. Then fire was set at the lower end of column with a gas-burner. It took 3 seconds to set fire. Thus, the vertical sample fiber assembly was made burnt from the bottom to the top.
The relationship between the weight of sample fiber assembly and the elapsed time was made known on various types of fiber and on different degrees of porosities. This relationship varies greatly with the kind of fiber in the case of the same degree of porosity. In general, the greater the degree of porosity, the larger the rate of burning; the burning was completely impeded at a critical degree of porosity for each fiber assembly. The assembly of cellulosic fibers has fairly large critical degree of porosity compared with that of acetate and acrylics.抄録全体を表示PDF形式でダウンロード (401K)
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