Thermosetting polyester amides were examined under the inert gas or vacuum state at 100_??_220 °C, for condensation polymerization abilities of ammonium salts formed by the reaction of amino alcohol (such as ethanol amine) with aliphatic dicarboxylic acids, e.g. oxalic, malonic, succinic, glutaric, adipic, pimelic, γ-keto pimelic, suberic, azelaic, sebacic, nona methylene dicarboxylic, deca methylene dicarboxylic and mixed acids (such as mixture of undeca methylene dicarboxylic and dodeca methylene dicarboxylic acid). Formation of these salts from dicarboxylic acids having an odd number of methylene groups were difficult owing to hygroscopic properties, and the resulted salts gave low melting point polymers compared with even number's dicarboxylic acids. Polyester amides prepared from dicarboxylic acid of a chain length less than 5 (such as pimelic and γ-keto pimelic acids) gave unsuitable polymer; on the other hand, in the case of chain length ware than 6 (such as suberic acid), it gave a suitable polymer possessing fiber forming properties except azelaic acid. Especially, in the case of long chain dicarboxylic acids (such as 8 and 10) it possessed excellent fiber forming and cold drawing properties. A further description on the visual observations, polymer melting temperature and solubilities is given.
Linear ester amide polymer was made by polymerizing, melt spinning and cold drawing process from 400g. of β-hydroxy ethyl ammonium sebacate. Mechanical and physical properties were studied and the following results were obtained. Drawn fiber was not coloured and lustrous monofilament of 30_??_40 denier. An X-ray diffractive examination of drawn specimen showed a fibrous pattern. The break strength and wet-dry ratio of break strength were 2.87g/denier and 64% respectively. The elongation of drying state was 10_??_25%. The density at 20°C was approximately 1.12. The melting point was 115°C. The moisture contents at R. H. 65% of the drawn and of the undrawn fiber were 1.3 and 1.5% respctively. And a noticeable decrease of mechanical strength after 1 year was observed. It may be concluded therefore that from the industrial view the fibre has no significant value due to its low melting temperature.
Linear ester amide copolymers were made from β-hydroxy ethyl ammonium sebacate (I) and salt which were prepared from polymethylene dicarboxylic acid (II) and polymethylene diamine (III) by the equimolar reaction. The polymethylene diamine (III), which have 2_??_12 methylene groups, except for 3 methylene groups, were made dy reduction of aliphatic dinitriles using Raney Ni catalyst. Suitable polymers were not obtained from dicarboxylic acids (II), which has less than 5 carbon chains, due to the accompanied depolymerization. When ethylene diamine was used as diamine, it gave the rubber-like polymer. The melting point of the polymer was over 203°C. Copolymers from (I) and of polymethylene diammonium sebacate (salt of (II) and, (III)), which have more than 4 carbon chains, could be spun very easily from molton state into light coloured or non-coloured and lustrous monofilament of 20_??_150 denier. It was drawn mechanically to 4.5_??_6 times as long as its original length without delay, the tensile strength of all fibers obtained by above method lay in the range of 1.0 to 3.2g/denier and the melting points lay in the range of 149 to 198°C. Diamines which have the odd number of methylene groups give the series of copolymers which have lower melting point and lower value of strength as compared with the groups of diamines which have the even number of methylene. The most excellent copolymers were made from β-hydroxy ethyl ammonium sebacate and tetra methylene diammonium sebacate. The tensile strength of the copolymer was 1.9_??_3.2g/denier and melting point 198°C.
Polyvinylalcohol fiber which is mixed-spun with polyethyleneimine was acetalized with various aldehydes. The following results were obtained. (1) The degree of acetalization depends generally on the electron-attracting power of atomic group attached to the aldehyde group. If the aldehyde molecule, however, has bulky and complex structure, the acetalization proceeds with some difficulties. (2) Polyvinylalcohol fiber which is a mixed-spun with polyethyleneimine has very good property in dyeing with acid or acid mordant dye. Moreover, the elastic behaviour of the fiber is appreciably improved when hydrophobic atomic group is introduced to the fiber by acetalization.
As previously reported swelling degree in acetic acid at room temperature and successive acetylation rate of cotton were remarkably decreased by immersion in aqueous solutions of NaOH, washing by water and drying. But when the imbibition water in alkali treated cotton was displaced by benzene and dried, then such a cotton could be smoothly acetylated after the same swelling treatment. Even the alkali treated and dried cotton without displacement of imbibition water could be smoothly acetylated after swelling treatment by water or hot acetic acid. Based upon these observed results the changes of fine structure of cotton accompanied with these treatments was also discussed.
Viscose rayon was hydrolysed and dried ditectly or after treatment by 1% aqueous solution of NaOH at 100°C. These fibers were acetylated after sufficient swelling pre-treatment, and it was observed that hydrolysed fibers were acetylated at higher rate than raw fibers in spite of their higher crystallinity. And hydrolysed fibers were smoothly acetylated compared to raw fiber after drying and swelling treatment under the same condition. Based upon these observations some discussions were made on the relation between accessibility for acetylation and fine structure of fibers.
Structures of cellulose gels were studied in relation to the coagulating conditions, with the help of model filaments or films whose structures are homogeneous. The gel structure was evaluated by putting together multifarious experimental results which differ in the physical mean; lateral-order distribution, accessibility, equilibrium absorption of dye, and density. And the following interpretations were set up: (1) In view of the multiplicity in the structural features of cellulose substances, it need hardly be considered that the structure should be examined together in both macromolecular and fine structural senses. (2) The structure of the primary xanthate gel frame acts the decisive part upon the macromolecular structure of cellulose gel resulting from it by regeneration. (3) The rate of coagulation seems to be of essential importance for the structure of the developing gel. (4) The zinc xanthate gel coagulated directly by zinc ion, have a different macromolecular structure from the zinc xanthate gel prepared by immersing the ammonium or sodium gels in a solution of zine sulphate. Thus, the application of the model experimental method, such as that proposed by Briggs, should be done carefully.
In order to dertermine the positions of substituent groups, the samples of cellulose xanthate were converted into methyl celluloses according to the method of Lieser, and the hydrolyzates of these methyl celluloses were analyzed by means of the paper-chromatography. The carbohydrates which could be identified were glucoses, mono- and di-methyl glucoses. After mono-methyl and di-methyl glucose fractions were separated by extracting separately with water from the filter-paper, each fraction was further fractionated into isomers by using the paper-chromatographic method. The molar fractions of each constituent for the cellulose xanthate of γ-value 82.2 were as follows glucose=0.35, 2-0-methyl glucose=0.40, 3-0-methyl glucose=0.02, 6-0-methyl glucose=0.06, 3, 6-0-methyl glucose=0.11 The reactivity of the hydroxy groups in the gyranose ring was discussed.
A new method for determination of pentosans in pulps by means of UV Absorption spectrum is described. This method is based on the experimental results, that UV Absorption spectrum of the distillate of pulp with 12% HCl is an additive of two spectra. One is the spectrum of furfural converted from pentosans and the other the products from glucose by the 12% HCl distillation (this is refered to as glucose component). Furfural and glucose components from pulp can be determined quantitively by analysing algerbraically the absorption of spectrum the distillates of pulp, using the UV absorption spectra of fulfural and glucose components which are obtained preliminary. Here absorptions are measured at two or more wave lengths, which may be called a “multi-points” method. The ratio of glucose component of the pulp determined by this method to that of pure glucose is called as “glucose number”. The glucose number is a value of the parts, reacted as glucose of pulp during 12% HCl distillation and also shows the accessibility of pulp. The spectroscopic method suggested by Smith and Rogers is based on the colorimetric method using aniline acetate, which is specific for furfural only, and is generally considered suitable for the determination of pentosan in highly purified pulp. The new method is based on the results of the absorption spectrum only. The glucose component contains, besides 5-hydroxy methyl-furfural (HMF), some amount of furfural converted from glucose. Therefore the values obtained by colorimetric method shows the total of furfural from pentosan and glucose (cellulose). On the other hand this method gives the value of furfural from pentosan only, regardless of the accessibility of pulp according to the above principles. Applying these methods for many kinds of pulps, the results obtained are as follows: 1. Pentosan values obtained by this new method agrees not only with those obtained by colorimetric method but also, with those of Smith-Rogers. 2. The glucose number has almost the same value in case of pulps only, and also agrees with the experimental results of Smith's, who described that the amount of 5-hydroxy-methyl furfural from pulps is almost constant. 3. Since the glucose number of pulp is as small as 0.3 furfural converted from cellulose (in pulp) can be practically neglected. Therefore it is found that the colorimetric method even though it is disadvantageous as shown above, can give satisfactory results for pentosan content in pulp.
The effects of the accessibility of cellulosic materials on the pentosan values are studied. Colorimetric method with aniline acetate, Smith's method with UV Absorption spectrum and the multi-points method previously suggested by the authors are used for determination of pentosan content of the following six samples; linter pulp, sulphite pulp, viscose rayon and dissolved samples of each in 42% HCl solutions. The following results are obtained experimentally. 1. In the case of colorimetric method and Smith's method, the pentosan value obtained is affected by the accessibility of cellulosic material, especially the latter. Therefore these two methods are applied only to the samples such as pulps, which have low accessibility, are not generally applied to samples such as rayon. 2. Contrary to above, the multi-points method is not affected by the accessibility of samples, but can determine the furfural formed from pentosan selectively. Therefore this method can be applied for the determination of pentosans in cellulosic materials regardless of its accessibility.
The basic testing instrument for which resilience meter was developed is composed of a stess measuring system. using magnetostriction gauge, a constant-rate of elongation drive for sample, and two wattmeters to integrate the stress with respect to time. The electronic system of the instrument is constructed with the following elements: Oscillator for magnetostriction gauge, amplifier, rectifier, chopper (DC-AC type), amplifier, power amplifier and photocell system for the revolution counting of wattmeter's disc. This instrument replaces the planimeter for measuring areas under the stress-strain curve, and the area under the curve during the loading cycle is measured by one wattmeter and the one of the unloading is measured by the other. Resilience, toughness, breaking energy, energy loss and other deformation energes of the fiber system can be measured by this meter.
The effect of gamma radiation on some of the physical properties of polyvinyl alcohol (PVA) fibers was measured. When irradiated in air, not formalized PVA fibers demonstrated only a small change in tensile strength at 107γ, but formalized fibers lost about 50% of their initial tensile strength. Draw ratio had an influence on the loss of the tensile strength of formalized fibers. The resistance to hot water was influenced only slightly. When irradiated in water, aqueous solution of ammonia, monoethanol amine and aniline, formalized fibers almost retained their initial tensile strength. The effect of irradiation on the tensile strength of PVA fibers acetalized by other monoaldehydes was almost the same as that of formalized fibers, but fibers acetalized by dialdehydes were outstanding in its resistance to changes in tensile strength at 107 γ.
It is expected that adsorbability of metal by wool will be changed when wool is degraded with alkali. The wool, treated with alkali for different length of time were used. The adsorption of Hg by wool was greatly increased when the wool was treated with alkali, while the adsorption of Ag by wool decreased, and that of Cu was kept constant, in the earier part of treatment. Hg curve had a peak in it. Cation exchange capacity of wool became greater as the time of treatment became longer, while anion exchange one was kept constant or less than that of non-treated. Adsorption of Hg or Ag by wool had a close relation to the lability towards alkalies of the disulfide groups is the cystine of the wool, but adsorption of Cu did not. The metal adsorbed by wool could be easily displaced by washing with acid.
The solubilities of dyes and effects of dyeing raw silk were determined using condensed phosphates and metasilicate as assistants. The results obtained are as follows: 1) The solubilities of direct and basic dye become saturated and attain equilibrium at 70°C. In the case of acid dye, its solubility is proportional to temperature. 2) The solubility of direct dye is proportional to temperature, when sodium triphoshate or pyrophosphate is used as assistant. As regards polymetaphosphate, the solubility is proportional to its amount used, whereas metasodium silicate shows reverse behaviour. 3) Temperature has little effect on the solubility of acid dye mixed with any one of these salts, and as the amount of salt added increases so does the solubility. 4) Similarly, regarding basic dye, temperature has little effect on its solubility, but as the amount of salt added increases the solubility decreases. 5) In dyeing raw silk, direct or acid dye when used with excess amount of any salt shows unfavourable dyeing power regardless of the type of salt. 6) Any one of the phosphates when used with basic dye gives the colour undesired and some precipitates result from the unknown reactions which occur in the dyeing process.
In the previous paper, we have seen that monomeric CH2CHCOOH could be_??_-polymerized with H2O2 alone as catalyser, but polymer yield was not high (40_??_50%). In this report, we studied redox polymerisation with H2O2 and various reducing agents combinations. We used the following reducing agents i.e. Na2S2O3, NaHSO3, Na2S2O4, Na2SO3 & (NH2)2H2SO4, as they all have minimum danger of discolouring the polymer. The following results are obtaind: 1) Na2S2O3 is the most effective. 2) In polymerizing at 40°C, and with H2O2 concentration 0.21mal/l, Na2S2O3 concentration of 0.0038mol/l is sufficient, and the 100% yields of polymeric CH2CHCOOH is obtainable.
The diffusion of dyes within the fiber in the mixture dyeing is discussed from the view point of the thermodynamic of irreversibl processes. The reciprocal coefficient is obtained from the apparent diffusion coefficient of each dye. It is shown that the concentration distribution of each dye in the fibre and each total amount of dye absorbed depend on the diffusion coefficient of each dye, the reciprocal coefficient between dyes and the ratio of equilibrium concentration of each dye. The behaviour of two dyes in the mixture dyeing especially depend on the reciprocal coefficient between them.
The general principle was previously discussed (J, Soc. Textile and Cellulose Industries, Japan, 14, 49, 1958) on the correlation between energy and entropy of dyeing, which led to; ΔH=m+nΔS where ΔH: energy of dyeing ΔS: entropy of dyeing m, n: constant The general correlation between ΔH and ΔS is also established on dyeing of the other fibres, such as cotton, viscose rayon, Nylon and Acetate by the substantive and the disperse dyes, cited from the other papers. Then, the consideration was given on the meaning of the constants m and n in the correlation formula whose dimensions are energy, and temperature respectively. Anyhow, an introduction of the new concept is necessony in order to understand this rule. At the same time, the difference of dyeing behaviour between Azo and Anthraquinoid types on the disperse dyes is discussed.