COMPOSITIONS ON THE BASIS OF SALTS OF POLYVALENT METALS AND ORGANIC-MINERAL INGREDIENTS FOR DYEING OF TEXTILE MATERIALS

ABSTRACT

This article presents the results of research on the development of dye compositions based on salts of polyvalent metals for dyeing natural fibers and their application in dyeing the textile materials on their basis.

АННОТАЦИЯ

В статье приведены результаты исследований по разработке красящих композиций на основе солей поливалентных металлов для крашения натуральных волокон и их применение в крашении текстильных материалов на их основе.

Keywords: protein fibers, dyeing, dyeing composition, polyvalent metal salts, phenol derivatives, the technology of dyeing, color characteristics, mechanism ofdyeing, color fastness.

Ключевые слова: Белковое волокно, крашение, красящая композиция, соли поливалентных металлов, производные фенола, технология крашения, цветовые характеристики, механизм крашения, прочность окраски.

Introduction. The development of the textile industry is caused by the development of new import- substituting materials and technologies. In this respect, the development of dye compositions that encourage the formation on fiber a coloration which is light, washing, abrasion land stains-proof, and dyeing technology of textile materials including synthetic, by them, without the use of dyes, the need for which is met only by importing them from Germany, Great Britain, Russia and other countries, due to the non-availability of aniline-ink industry in Uzbekistan, is present both scientific and practical interest. For dyeing the polyamide fibers mainly disperse, acid, acid-and metal-reactive dyes are used. In connection with the above, the goal of the research is to develop the dye compositions based on local raw materials and the technology of synthetic polyamide textile materials dyeing without application of special dyes, using the developed dye compositions, based on existing compositions in Uzbekistan.

In Uzbekistan, were silk is produced only a small part of the fibers are processed into finished products, and the main part is exported in the form of semi-finished product. One of the reasons for this situation is the absenceyin the country the necessary product needed to process the chemical materials, including dyes, due to the non-availability of aniline-ink industry in Uzbekistan

The dyeing of textile materials from natural fibers is performed by synthetic dyes obtained on the basis of a variety compounds that are also not available in Uzbekistan. In this regard, the establishment of the theoretical foundations of coloring the textiles from natura fibers, using local raw materials is important.

Objects and methods of research. The method of dyeing by synthesis on the fiber the organic dyes of low molecular weight compounds of simple structure is the most rational solution to intensification the dyeing process. This is because the molecules of the initial compounds, have almost no relatedness to the fiber, and because of the small geometric dimensions show high diffusion coefficient values in the fibrous substrate, thereby achieving the maximum colour penetration of fibers in the minimum time of its stay in the solution.

The subject of research was protein fiber, alkali and polyvalent metals salts, aromatic hydroxy compounds. The study of the physicochemical properties of the fibers and materials structure carried out by IR spectroscopy; spectrophotometry, chelatometry, pH analysis, X-ray diffraction, electron microscopy and other physical and chemical methods of analysis.

Protein fibers are high-molecular compounds, constructed mainly of acyclic, carbocyclic and heterocyclic amino acids and contain significant amounts of the amino and carboxyl groups, capable to enter into a reaction of nucleophilic and electrophilic substitution. Amines and carbonyls have the property of formation the coordination bonds. With polyvalent metals cations such as iron, nickel, cobalt, copper, which have their own chromophoric properties, they form colored complexes. The primary amino groups are able to diazotize with the formation of azo groups, which have highly activity and form vibrant complexes with cations of variable valence. The presence of amino acids containing aromatic rings (tyrosine, tryptophan) in the protein fibers allows the formation of complex compounds of chelated type with polyvalent metal cations.

In article [1, 2] the possibility of diazotization of wool and combining it with naphthols and naphthylamine for obtaining yellow and brown tones is shown. According to data from article [3] in the processing of wool and silk by nitrites, and then by the metal salts the nitrosation of tyrosine is happen and die resulting product forms complexes with metals. By this method the solid color can be obtained. Diazonium salts based on a number of aromatic amines are highly reactive to the combination of some amino acid residues of fibroin, especially tyrosine and histidine.

In article [4] is shown that the diazo compounds are combines with proteins, due to the presence in them of phenolic groups in tyrosine residues and the indole nucleus in tryptophan residues. At the fibroin is 13% of tyrosine from the amount of amino acid. When processing silk by diazo compounds in the presence of sodium acetate obtained coloring of yellow, orangey, brown and chestnut. These colors are close to the normal color of azo dyes derived from the combination of phenols. However, the amount of protein molecules greatly increases their resistance to light and wet treatments [5]. In an alkaline solution the tyrosine combined in one or both o-positions to the phenolic hydroxyl. The dye received on a silk fiber has an integrated nature. Fiber absorbs some of the diazonium salt, especially if it is taken with the excess anti two moles on one tyrosine residue.

The possibility of dyeing protein fibers by the solutions of copper, iron, cobalt and nickel salts has been studied. The results showed that the treatment of protein fibers by aqueous solutions of Cu²⁺, Co²⁺, Ni²⁺, Fe³⁺ metals salts, they become dull colors that are easily removes from the fiber during the subsequent Washing. Processing of protein fibers by Cu²⁺, Co²⁺, Ni²⁺, Fe³⁺ salt solutions in the presence of sodium nitrate contributed to the getting a bright and stable colors. Under the action of sodium nitrate on protein fibers in acid medium all amino groups of fiber are changing. Not exclude the possibility of a transition of some amino groups in the azo group and further interaction with transition metal cations with formation of complex compounds.   

Results of research and analysis. A number of transition metal ions, such as copper, nickel, cobalt, iron, chromium have their chromophoric properties, so they can form colored complexes with functional groups of the protein fibers. In this regard, by the earlier described studies have established the possibility of obtaining the compositions based on salts of polyvalent metals for dyeing the protein fibers. Developed two types of compositions: Compositions based on salts oi polyvalent metals, nitrate and sodium acetate; and compositions based on salts of polyvalenl metals, nitrate and sodium acetate and aromatic hydroxy compounds.

The influence of the concentration of iron salts, sodium nitrate and sodium acetate on coloristic characteristics of colored natural silk has been studied. Where x, у - the colot coordinates, p- lightness, A. - wavelength, P - saturation. As iron salts the ferrous sulphate has been selected. Data are presented in Table 1.

Table 1.

The influence of the powder dye composition ingredients concentration of ferrous sulphate on the color characteristics of the colored natural silk.

As can be seen from the data obtained, when changing the concentration of ferrous sulphate in the dyeing composition the colour hue of silk does not change, but only the saturation of colors is changed. The greatest richness has the colors containing iron salts in the composition in an amount of 40%. Based on these data the optimal content of a composition based on ferrous sulphate is: ferrous sulphate Fe₂(SO₄)₃ 9N₂O-40%, specimen-40%, СН₃СОONа-20%. Silk after dyeing becomes orange-yellow color.

The influence of the concentration of cobalt chloride, sodium nitrate and sodium acetate on coloristic figures of colored natural silk has been studied (Table 2).

Table 2.

The influence of powder dye composition ingredients concentration of cobalt chloride on the color characteristics of the colored natural silk

As can be seen from the obtained data, the composition based on cobalt makes possible the getting of a gray color with a yellowish tint. Color characteristics of colored silk dyed by the composition containing 40% of CoCI₂ 6H₂O has a darker gray color (lightness p = 17) than the composition containing 45% of CoCI₂ 6H₂O (lightness p = 31%).

Based on the conducted research has been established the optimal content of the composition based on CoCI₂ 6H₂O: C0CI₂ 6H₂O - 40%, specimen-40%, СН3СООNа - 20 %.

The influence of the concentration of ferrous sulphate, sodium nitrate, sodium acetate and resorcinol on coloristic figures of colored natural silk has been studied (Table 2).

Table 3.

The influence of powder dye composition ingredients concentration of ferrous sulfate on die color characteristics of the colored natural silk

Based on the conducted research has been established the optimal content of the composition based on ferrous sulfate: Fe₂(SO₄)₃ 9H₂О - 33%, specimen-20%, CH₃COONa 10%, aromatic hydroxy compounds - 37%.

The dye composition gives green color to the protein fibers.

The influence of the concentration of cobalt chloride, sodium nitrate, sodium acetate and resorcinol on coloristic figures of colored natural silk has been studied (Table 2).

Table 4.

The influence of powder dye composition ingredients concentration of cobalt chloride on the color characteristics of the colored natural silk

When increasing the concentration of cobalt in the dye composition the color hue ol dyeing material changes from orange-red to burgundy with a simultaneous increase of the saturation of colors produced. ,

Based on the conducted research has been established the optimal content of the composition based on cobalt chloride: CoCI₂ 6Н₂О - 29 %, specimen-24%, CH₃COONa -10 %, aromatic hydroxy compounds - 37 %.

By IR-spectroscopy and spectrophotometry was found that when processing of protein fibers by dye composition the amino groups of fibers interact with cations of input polyvalent metals or polyvalent metal complexes with phenols with formation of salt and coordination bonds, facilitating the creation of chelated structures. This causes the high strength of the compounds formed to wet processing and light.

From the obtained data is clear that by the action of nitrous acid the aminogroups of fibers pass into the azo group which by interaction with metal cations is form the complexes. As known, the azo group by itself is not able to give stable complexes with metals, if during this does not form a chelate bond. A necessary condition for the formation of chelate bond is the presence of hydroxyl, amino or other group in the o-position to the azo group. In accordance with rule of substitution in the benzene ring by the action of nitrous acid on phenols are formed the nitrosophenol that are not stable and they are converted to diazo compound during the reaction with nitric oxide, formed by the decomposition of nitrous acid. The presence of the hydroxyl group in the o-position to the azo group in phenols is allows the formation of chelate bond with polyvalent metal cations available in the dye compositions.

Conclusion: Based on the conducted studies were developed the optimum content of powder dye compositions based on salts of polyvalent metals for protein fibers and fabric dyeing technology based on them.

Thus, the treatment of textile materials based on protein fibers by compositions based on salts of polyvalent metals and aromatic hydroxy compounds contributes to the formation on the fiber the intensely colored complexes of polyvalent metal cations, one of the ligands of which are functional groups of protein fibers. The dye composition interact with the protein fiber with the formation a colored structures due to the salt and complex formation that provides high resistance to wet treatments, abrasion, light, dry cleaner and do not require the additional fixation.

References:

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2. Abdurakhmanova Sh.G., Negmatov S.S., Madjidova Sh.G. / Way of dyeing of proteinaceous fibers // Patent RU № IDP 04925.
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4. Shoxista Rasulova. Application of Infonnation Technology to Determine the Compound of Dyeing Compositions based on Transition Metal Salts. II Journal of Chemical Engineering and Chemistry Researches A 2014, July 25. pp. 40-46.
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