OBTAINING CHITIN AND CHITOSAN APIS MELLIFERA USING THEM IN THE PROCESS OF FABRIC DYING

ABSTRACT

Wide opportunities for using chemical transformations of chitin and chitosan to obtain a variety of the structure and properties of the materials make these polymers one of the most interesting and promising types of raw materials for various applications. The article presents the results of obtaining chitin using various methods and their use in the process of tissue coloring are presented. It is shown that chitosan can be used as an intensifier, reducing expensive dye and electrolyte, as well as temperature, when dyeing mixed fabrics with active dyes.

АННОТАЦИЯ

Широкие возможности использования химических превращений хитина и хитозана для получения разнообразных по структуре и свойствам материалов делают эти полимеры одним из наиболее интересных и перспективных видов сырья для различного применения. В статье представлены результаты получения хитина и хитозана различными методами и их использование в процессе окраски тканей. Показано, что хитозан можно использовать в качестве интенсификатора, позволяющего снизить количество дорогостоящего красителя и электролита, а также температуры при крашении смесовых тканей активными красителями.

Keywords: chitin, chitosan, natural biopolymer, deproteinization, demineralization, intensifier, dyeing, silk and cotton-silk fabric.

Ключевые слова: хитин, хитозан, природный биополимер, депротеинизация, деминерализация, интенсификатор, крашение, шелк и хлопчатобумажная ткань.

INTRODUCTION.  Recently, due to the growing requirements for the quality of manufactured products, there has been a tendency to create economical and resource-saving technologies that make it possible to obtain competitive textile products [1].

To improve the quality of textile products, you can use the natural polymer chitosan, obtained from completely renewable raw materials like krill shells, crabs and other crustaceans. Its use is known for dyeing cotton fabrics with direct and active dyes to improve the dyeability of textile material [2]. Chitosan is a biologically active polysaccharide of natural origin, which has a complex of valuable properties in practical terms and attracts the increasing attention of researchers around the world. The interest of specialists working in the field of textile chemistry in chitosan is due to its properties such as biodegradability, non-toxicity, good film-forming and thickening properties, and the ability to fix without reagents on natural fibers. Due to these properties, chitosan can be considered a promising finishing material for refining textile products and imparting new special properties to them [3]. Chitosan is the most well-known and studied water-soluble derivative of chitin. Chitin is a natural biopolymer of animal origin, which is second only to cellulose in terms of prevalence and is reproduced from completely renewable natural raw materials (fig.1.).

Figure 1. Chemical structure of chitin and chitosan

Chitin is part of the supporting tissues and external skeleton of arthropods (crustaceans, arachnids), insects, and algae, where it is found in a complex with mineral salts [4]. However, despite its availability, the practical use of unmodified chitin is constrained by its poor solubility. There is no standard process for chitin deacetylation (CT), however, most traditional methods use concentrated solutions of sodium hydroxide in a wide range of concentrations from 35 to 50%, temperatures from 20 to 140 ^oC, hydro modules from 3:1 to 10:1, treatment times from 0.5 h up to 10 days. Chitin can be obtained in various ways like chemical, biological, electrochemical, etc.

1. The chemical method is based on deproteinization, demineralization and depigmentation using chemical reagents like acids, alkalis, peroxides, etc. [5]

Demineralization is usually carried out using hydrochloric acid (HCℓ) at normal temperature to reduce the risk of hydrolysis of the chitin chain. The bleaching method for chitin is the process of bleaching with hydrogen peroxide (H₂O₂) in case there is a need.

2. The biotechnological method involves the use of enzymes for deproteinization of raw materials, for demineralization and chemical reagents for depigmentation [6].

To achieve a high degree of deproteination, the most effective methods are those involving the use of enzymes and enzyme preparations of microbiological and animal origin, such as pancreatin, acid proteinases, alkaline proteinases [7].

The most interesting direction for obtaining chitin is the process of lactic acid fermentation of the shell. As a result of this process, the degree of deproteinization and demineralization of chitin is 90 and 80%, respectively.

3. The electrochemical method is an alternative to the chemical and biotechnological ones, which makes it possible to obtain chitin of a sufficiently high degree of purification and nutritionally valuable proteins and lipids in one technological process.

The essence of the technology for producing chitin by the electrochemical method consists in carrying out the stages of deproteinization, demineralization and providing shell-containing raw materials in the form of a water-salt suspension in electrolyzes with an original design under the influence of an electromagnetic field, a directed flow of ions and a number of low molecular weight products formed as a result of the electrolysis of water H+ and OH^- ions , which determine the acidic and alkaline reactions of the medium and its redox potential, respectively.

MATERIAL AND METHODS.  The complex of the analyzed sources makes it possible to obtain natural polysaccharide chitin with a number of unique properties, due to the fact that it is an intermediate polymer in the synthesis of a widely used chitosan derivative (ChD), which has its own biological activity, reactivity and film-forming properties.

The process of deacetylation of chitin has a number of features. For example, for the synthesis of highly deacetylated chitosan, a tenfold molar excess of  NaOH is required, and the deacetylation process proceeds most rapidly during the first hour of the reaction, when the degree of acetylation (DA) reaches 0.15, then the reaction slows down and achieving lower SA values requires additional treatments or retreatment with sodium hydroxide solution.

The harsh conditions of the deacetylation reaction cause:

• polymer degradation;

• change in its supramolecular structure;

• environmental pressures on the environment;

• a significant increase in the cost of chitosan, limiting the possible areas of its use.

The reason for the difficulty of deacetylation to SA below 0.2-0.25 is the ordered supramolecular structure of chitin and the inaccessibility of the remaining N-acetyl groups for the action of NaOH unless particularly harsh conditions are used

Recently, interest in mixed fabrics has increased, since in different areas of human activity, fabrics of absolutely different fields of application are needed, differing not only in purpose, but also in physical and mechanical properties. Blended fabrics are produced primarily in order to increase the level of strength and wear resistance, which is accompanied by an improvement in hygienic properties, breathability, resistance to pollution, resistance to damage by microorganisms, elasticity, crease resistance, easy washing and ironing, and quick drying [8].

Today, the importance of searching for new improved methods for obtaining a promising natural amino polysaccharide, chitosan, from local resources is obvious; it opens up broad horizons for studying its properties and using it in the textile industry as a thickener [9–10] in printing and an intensifier for dyeing various materials [11–12].

The study used chitosan synthesized from dead bees Apis Mellifera in the scientific laboratory of TSTU [9-12], Silk and Cotton-silk fabric (base silk, weft cotton 55/45) produced at the joint venture Bukhara-China JSC ‘Bukhara Brilliant Silk,’ as well as an anionic dye ‘Active bright blue K (reactive blue K).’

RESULTS AND DISCUSSION. In our studies, we used chitosan as an intensifier for dyeing silk and cotton-silk blended fabrics.

In solution, chitosan acquires a positive charge due to the amino group, since the fibers and most of the dye in solution have a negative potential.

The study of the processes occurring between water-soluble dyes and the chitosan film, as well as the possibility of interaction between the chitosan film and the tissue, is of great importance, since it allows one to judge the nature of the bonds that arise in the ‘tissue - chitosan - dye’ system, which can largely determine the quality of coloring. when coloring textile materials.

 A 2% solution of acetic acid was used to dissolve chitosan. In this work, a solution of chitosan (0.5–1.5 g/l) was used to treat tissues before the coloring process (Table 1).

Table 1.

It is known that silk is dyed with active dyes according to the acid and alkaline methods, depending on the nature of the dye, the degree of their fixation depends on the chosen method. Dyeing of natural silk with active dyes is carried out according to the periodic technology according to the alkaline method in two stages fig.2.

Figure 2. The technology of dyeing cotton-silk fabrics using chitosan according to the periodic method

Figure 3. The technology of dyeing cotton-silk fabrics by the semi-periodic method

In the second stage, in a slightly alkaline medium (at pH 10.0-10.5), a covalent bond is formed between the dye and silk fibroin, which ensures high color fastness to washing. Therefore, further studies were carried out according to this method. Active bright blue K was chosen as the dyes. Chitosan concentration varied from 0 to 1.5 g/l. A solution of chitosan in acetic acid (2%) was applied to the fabric before dyeing and dried at a temperature of 100–110 °C until completely dry. Process implementation data and examples of results are shown in fig 3.

CONCLUSIONS.  1. Chitosan obtained from dead bees Apis Mellifera can be used as an intensifier, which allows you to reduce the amount of expensive dye and electrolyte, reduce the temperature; 2. When dyeing mixed fabrics with active dyes, the amino groups of chitosan react with the active dye to form hydrogen bonds; 3. Protonated NH³⁺ groups form ionic bonds with the anionic active dye and the OH groups of chitosan participate in the formation of hydrogen bonds with the amino group of cotton-silk fabric.

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