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Home / News / Industry news / Research Progress on Dyeing Methods Based on Chemical Reactions for Printing and Dyeing

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Research Progress on Dyeing Methods Based on Chemical Reactions for Printing and Dyeing

Ji Zhengfang¹², Jiang Hua³
(1. Zhejiang Hongyi Chemical Co., Ltd., Lishui 323700, China;
2. Zhejiang Daoyuan New Materials Co., Ltd., Lishui 323700, China;
3. Engineering Research Center for Eco-Dyeing and Finishing of Textiles, Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, China)

Abstract:
This paper introduces recent developments in novel reactive dyeing methods based on chemical reactions, including diazotization-coupling reactions, diazotization-nucleophilic substitution reactions, Mannich reactions, Maillard reactions, and carbene chemistry reactions. The principles, dyeing processes, and resulting dyeing effects of these methods are introduced. Their advantages and disadvantages are reviewed, and the future prospects of reactive dyeing techniques are also discussed.

Keywords: Reactive dyeing; Coupling reaction; Mannich reaction; Maillard reaction; Carbene insertion reaction

Classification Numbers: TQ619.1; TS193.5
Article ID: 1672-1179 (2024) 06-14-07
Document Code: A

Introduction
Dyeing not only imparts color to textiles but must also ensure sufficient color fastness for practical applications. In general, the stronger the interaction between dye molecules and fibers, the better the color fastness. Among all interaction types, covalent bonds are the strongest. For instance, when dyeing hydrophilic fibers such as cotton, reactive dyes usually exhibit better color fastness than direct dyes because reactive dye molecules can chemically react with hydroxyl groups on cellulose, forming strong covalent bonds with the cotton fibers.
In contrast, dyeing synthetic fibers like polyester primarily relies on disperse dyes. However, dye migration during polyester dyeing often affects subsequent processing, which stems from the weak interactions between dyes and fibers. Therefore, developing reactive dyeing methods tailored to fiber characteristics—establishing covalent bonds between dyes and fibers—holds great promise for achieving high fastness dyed products.

1. Dyeing Methods Based on Diazotization-Coupling Reactions

Diazotization refers to the reaction of aromatic primary amines with nitrous acid to form aromatic diazonium salts. Coupling reactions occur between these diazonium salts and phenols, amines, or compounds with active methylene groups to form azo structures. As a primary method for synthesizing azo dyes, diazotization-coupling reactions offer advantages such as low raw material costs, operational simplicity, and wide substrate compatibility.
If this reaction can be performed directly on fibers or fabrics, it eliminates the need for dye synthesis and purification steps, thereby directly imparting color to the material.

1.1 Silk

In silk fibroin proteins, tyrosine residues account for approximately 6% (mol)[1]. The ortho position of the phenolic hydroxyl group in tyrosine is electron-rich and, under alkaline conditions, can react with diazonium salts to form azo chromophores. Based on the coupling reaction between diazonium salts and tyrosine residues in silk fibroin (see Figure 1), Chen Weiguo et al. proposed a coupling dyeing method for silk[2].
They first treated silk fabric with a 10 g/L sodium hydroxide solution (100% wet pick-up), followed by immersion in a diazonium salt solution prepared from Red Base (2-amino-4-nitrotoluene), and reacted at 0–5°C and pH 4.5 for 15 minutes. The resulting dyed silk fabric displayed a fastness rating of 4–5 for soaping.

Figure 1: Schematic of coupling reaction between diazonium salt and tyrosine residue in silk fibroin

Yang Haiwei et al. used ortho-nitroaniline diazonium salt as the diazo component to explore optimal dyeing conditions and investigate thermodynamics, revealing the reaction patterns of diazonium salts with silk[3]. Alkaline treatment of silk reduces the Zeta potential of fibroin, facilitating diazonium salt adsorption, while also promoting dissociation of tyrosine hydroxyls into phenolate ions, enhancing the electron richness of the ortho carbon and boosting coupling reactivity.
The optimized dyeing conditions used diazonium salt in a 2:3 molar ratio to tyrosine residues, with a pH of 6.8 at 5°C for 45 minutes. The dyeing thermodynamics followed the Langmuir adsorption model (see Figure 2).

Figure 2: Adsorption isotherm of ortho-nitroaniline diazonium salt on silk

Since the tyrosine residue structure cannot be altered, the achievable color gamut in this method heavily depends on the structure of the diazonium salt. Research by Jiang Hua et al. showed that diazonium salts with electron-withdrawing groups can cause a significant red shift in dyed silk, producing orange-red colors. Using aromatic amines with extended conjugation, such as p-aminoazobenzene or 1-aminoanthraquinone, resulted in reddish hues[4]. However, due to the limitations of donor-acceptor type azo structures, blue and violet shades remain difficult to achieve.

Compared with acid or reactive dyes, coupling-dyed silk fabrics show superior color fastness. However, the method has clear drawbacks: silk must endure strong acidic or alkaline conditions, inevitably causing damage to the delicate fiber. Moreover, the limited azo structure restricts the color range, especially for blue and violet shades, and no effective solution currently exists.

1.2 Meta-Aramid

Meta-aramid is a high-performance fiber formed by the polymerization of isophthaloyl chloride and meta-phenylenediamine. In the chemical structure of meta-aramid, the meta-phenylenediamine unit has two secondary amino groups that exhibit some electron-rich properties. These two secondary amino groups act as electrophilic substitution reaction sites, making them prone to coupling reactions at the ortho or para positions. The meta-aramid structure contains two types of meta-phenylenediamine units: terminal meta-phenylenediamine and middle meta-phenylenediamine. One amino group in terminal meta-phenylenediamine is a free amino group, which is electron-donating, making it prone to coupling reactions with diazonium salts at the para position.

In theory, using dyes containing aromatic amine structures can also undergo coupling reactions with silk after diazotization, but the dyeing process needs adjustment. If the aromatic amine dye is diazotized first, and then the scoured silk is immersed in the diazonium salt solution, the diazonium salt will quickly undergo self-coupling reactions, rather than coupling with the silk. To solve this, Jianghua et al. adopted a dyeing-diazotization-coupling process: first dye the aromatic amine dye onto the silk fabric, then perform the diazotization reaction on the fiber, and finally adjust the pH to alkaline, allowing the formed diazonium salt to immediately react with the silk, thus improving the color fixation rate [5]. The fixation rate of dyes like C.I. Acid Brown 4, C.I. Acid Green 20, etc., when used to dye silk fabric, can reach over 80%.

To solve the problem of incomplete chromatographic results, Cui Zhihua et al. proposed another coupling reaction dyeing method [6]. They modified silk with indigo acid anhydride to give the silk aromatic amine groups, then performed diazotization on the modified silk, forming diazonium salts on the silk, and finally treated the fabric with coupling components like H acid to form azo chromophores, thus giving the silk colors like yellow, red, and green (Fig. 3). The color fastness to soap washing and rubbing of the dyed silk fabric can reach level 4-5 or higher.

Fig. 3 Modification of silk with indigo acid anhydride and its coupling reaction schematic.

The meta-phenylenediamine in meta-aramid is influenced by the carbonyl group, which reduces the electron density, making it less favorable for coupling reactions. Based on this, it is speculated that strongly alkaline aromatic amine diazonium salts can only act on terminal meta-phenylenediamine, but since terminal meta-phenylenediamine is sparse, the number of azo chromophores formed is limited, resulting in light colors. Weakly alkaline aromatic amine diazonium salts can further react with the abundant middle meta-phenylenediamine units in meta-aramid, resulting in deeper, more intense colors (Fig. 4).

Jianghua et al. confirmed the coupling dyeing mechanism of meta-aramid and provided a corresponding dyeing method [7]. They first treated meta-aramid in dimethyl sulfoxide at 55°C for 30 minutes, then reacted the weakly alkaline aromatic amine diazonium salt with the meta-aramid in methanol, producing red-brown dyed fabrics. Although meta-aramid's coupling dyeing method still faces challenges such as limited color variety, the use of organic solvents like dimethyl sulfoxide and methanol, and the difficulty in preparing weakly alkaline aromatic amine diazonium salts, it remains effective for identifying meta-aramid, particularly in distinguishing it from para-aramid [8,9].

Fig. 4 Schematic diagram of the coupling reaction between weakly alkaline aromatic amine diazonium salts and meta-aramid macromolecules.

1.3 Cotton

Cotton's basic component is cellulose, which lacks electron-rich sites for coupling reactions. Therefore, cotton fabrics cannot directly undergo coupling dyeing to obtain color. Traditional ice-dyeing (Azoic Dye) methods can conduct coupling reactions on cotton fabrics, but they require first applying color phenols (the coupling component, also known as the base agent) onto the cotton fabric before using the color base (also called color salt) for dyeing. The famous "National Flag Red," which is included in national archives, is an example of such an ice-dyeing method [40]. Though this dyeing method offers high color fastness, it also produces significant pollution. The dye molecules on the fabric still rely on weak forces or physical mechanical interaction with the fibers, so under harsh conditions like organic solvents or high temperatures, the dye molecules may detach from the fibers.

Jianghua et al. proposed modifying cotton fibers with aniline derivatives through triazine-type active groups, thus enabling cotton fabrics to undergo coupling dyeing (Fig. 5) [10].

Fig. 5 Schematic of the coupling dyeing mechanism for cotton fabric modified with aniline derivatives.

They used compound 1 to create a printing paste, applied it to cotton fabric, and then used steam to promote the modification of the cotton fibers. Subsequently, the fabrics were dyed with diazonium salts such as 4-nitroaniline diazonium salts, 2,6-dichloro-4-nitroaniline diazonium salts, and 2-amino-5-nitrothiazole diazonium salts, resulting in dyed cotton fabrics in colors like orange, red, and blue. The dyed fabrics exhibited excellent resistance to organic solvent extraction, better color fastness, and superior color retention compared to those dyed with traditional ice-dyeing or reactive dyes.

2. Cotton Dyeing Method Based on Aromatic Amine Dye Diazotization-Nucleophilic Substitution Reaction

Bhate et al., based on the nucleophilic substitution reaction between diazonium salts and hydroxyl compounds, proposed a method in which aromatic amine dyes are applied to cotton fibers, then converted into diazonium salts, which react with the hydroxyl groups on cellulose to achieve reactive dyeing (Fig. 6) [11].

Fig. 6 Schematic of the diazotization-nucleophilic substitution reaction of aromatic amine dye on cotton fabric.

They confirmed the feasibility of this reactive dyeing method using self-made γ-acid or J-acid type dyes. Jianghua et al.'s research showed that first, the dye and cotton fabric were heated at 90°C in sodium chloride solution (8 g/L) for 30 minutes, then cooled to 0°C for diazotization reaction for 10 minutes. Afterward, sodium carbonate (6 g/L) was added, and the mixture was stirred at room temperature for 10 minutes to securely bind the dye to the cotton fabric [12]. Bhate et al. further used bisamine direct dyes to dye cotton fabrics and proposed a multi-bath continuous padding dyeing process [13,14]. The dyeing, diazotization, and nucleophilic substitution reactions were conducted in separate baths, keeping them isolated and unaffected, which facilitated the reuse of the dye baths. Compared to conventional reactive dyeing methods, this method requires only an additional diazotization reaction. However, it is necessary to control the acid quantity to avoid damaging fiber strength. Additionally, compared to the dye's original color, the dyed cotton fabric exhibits a red shift, as the amino groups of the aromatic amine dye turn into ether bonds, narrowing the energy gap of the chromophores, leading to the red shift in the color.

3. Dyeing Method Based on Mannich Reaction

The Mannich reaction, a three-component condensation reaction involving compounds with strongly acidic methylene groups, primary or secondary amines, and aldehydes or ketones, leads to the formation of amine alkylated derivatives [15]. Considering that silk fibroin proteins have tyrosine residues with phenolic groups, applying aromatic amine dyes and aldehydes to silk, based on the Mannich reaction principle, could result in reactive dyeing of silk with aromatic amine dyes (Fig. 7).

Fig. 7 Schematic of the Mannich reaction principle for dyeing silk with aromatic amine dyes.

Chen Weiguo and Cui Zhihua et al. conducted in-depth studies on this method [16-24]. They demonstrated that silk could be dyed by the Mannich reaction by immersing it in a dye bath containing aromatic amine dyes and formaldehyde under weak acidic, room temperature conditions for 10 hours. This method produced silk fabrics with excellent resistance to soap washing, with simple operation, significant color fixation, mild dyeing conditions, minimal damage to silk, and low energy consumption, making it promising for industrial applications. However, some issues remain, such as the need for excessive formaldehyde, which poses a risk to operators. Substituting formaldehyde with acetone aldehyde can reduce toxicity, but the dyeing performance is not as good as with formaldehyde [18]. Moreover, the method requires a long time, lowering production efficiency. Raising the temperature can shorten the process but sacrifices some dyeing rate and color depth [20]. Also, only a limited number of commercially available aromatic amine dyes can be used, necessitating the development of a complete dye system to meet color demands.

4. Dyeing Method Based on the Maillard Reaction

The Maillard reaction is a non-enzymatic browning reaction widely present in food processing. It involves the interaction between carbonyl compounds (reducing sugars) and amino compounds (amino acids and proteins), undergoing complex processes such as rearrangement, polymerization, and condensation, ultimately forming brown or even black macromolecular compounds known as melanoidins. This reaction, also referred to as the carbonyl-amino reaction, has long been utilized in the food industry for controlling the color of products in fields like baking, coffee processing, meat processing, fragrance production, and brewing. Dyeing professionals have speculated whether the Maillard reaction can be applied to color fibers containing amino groups [25-30].

Ohe et al. confirmed that fibers containing amino groups, such as wool, silk, and nylon, can acquire color through the Maillard reaction [25]. Among them, wool exhibited the best coloring effect (Figure 8). For instance, when wool, silk, and nylon were immersed in a 0.1 mol/L xylose aqueous solution at 100°C for 4 hours, wool achieved a K/S value of 3.8, while silk and nylon only reached K/S values of 0.48 and 0.86, respectively [25]. Therefore, research on the Maillard reaction dyeing of wool has been the most extensively reported. The dyeing method using the Maillard reaction has several advantages, such as simple operation, good wash fastness on wool, inexpensive and safe raw materials, easy wastewater treatment, and no need to prepare dyes. However, there are also significant drawbacks, including slow reaction rates that require a long time for color change to occur, limited color variety that is not very vibrant, and poor light fastness. Currently, related expansion research focuses on optimizing the Maillard reaction dyeing method in terms of raw materials and processes to achieve practical application. Additionally, researchers are applying the Maillard reaction principle to graft antimicrobial or antioxidant substances onto wool fibers, imparting more functionality to the dyeing method.

Figure 8 Schematic diagram of the Maillard reaction principle of reducing sugar on wool dyeing

5. Dyeing Method Based on Carbine Chemical Reactions

Carbine-type dyes and their insertion reaction principle for dyeing synthetic fibers.

Figure 9 Schematic diagram of the insertion reaction principle of carbene dyes for dyeing synthetic fibers

Carbines refer to a class of substances where the carbon atom has only six valence electrons. The simplest carbine is the methylene group (∶CH2). Carbines are highly reactive and can undergo various types of chemical reactions, such as intramolecular rearrangements, dimerization, and intermolecular reactions like insertion and addition. The insertion reaction of carbines refers to the reaction in which a carbine inserts itself into C-H, N-H, or O-H bonds, forming new C-C, C-N, or C-O bonds. Based on this, Lee et al. introduced the para-toluenesulfonylhydrazone structure into dye molecules and treated them with n-butyllithium to obtain a new reactive dye (Compound 2 in Figure 9) [31,32]. This dye, when subjected to high-temperature treatment (140°C), releases the para-toluenesulfonylhydrazone unit to form a carbine intermediate, which can then react chemically with C-H bonds on synthetic fibers such as polypropylene, thus firmly binding the dye chromophore to the synthetic fiber. This new type of reactive dye can be referred to as a carbine-type dye. However, carbine-type dyes based on para-toluenesulfonylhydrazone structures have several drawbacks, including inconvenient dye synthesis, poor dyeing performance, low atom economy, and environmentally harmful by-products.

Jiang Hua and Zhao Tao et al. designed and developed a series of carbine-type dyes based on the structure of bisacridine (Compound 3 in Figure 9) [33-36]. These dyes, upon high-temperature treatment, form carbines by releasing nitrogen molecules, significantly improving atom economy and producing more environmentally friendly by-products. Their application is highly effective, with the dyes reacting chemically with various synthetic fibers such as polyester, polypropylene, aramid, acrylic, nylon, and spandex to achieve dyed synthetic fiber fabrics with high color fastness. Jiang Hua et al. further explored the feasibility of using α-phenyl diazonium ester structures as carbine precursors, and the developed dye (Compound 4 in Figure 9) exhibited excellent dyeing fastness on spandex [37]. Carbine-type dyes and their corresponding dyeing methods are still in the preliminary exploration stage, with limited dye structures, unclear dyeing fastness mechanisms, and a need for further research into their structure-activity relationships to establish a solid foundation for the practical application of these dyes.

6. Other Reactive Dyeing Methods for Spandex

After polymerization, polyurethane may contain trace amounts of isocyanate groups. Based on this, Hanna proposed a reactive dyeing method for polyurethane elastomeric materials, with the reaction mechanism shown in Figure 10 [38].

Figure 10. Reaction Mechanism of Amino Dyes with Polyurethane Materials

This method uses amino-containing dyes to dye freshly made polyurethane materials. The amino group in the dye reacts with the residual isocyanate groups on the polyurethane, thus binding the dye to the polyurethane material. The dyeing procedure is as follows: the polyurethane material is placed in a perchloroethylene solution of the dye, with a bath ratio of 1:50 and dye concentration of 1 g/L, followed by boiling at 121°C for 60 minutes to obtain the dyed material. The author used C.I. Disperse Black 1 for dyeing experiments, and the dyed polyurethane’s color remained intact after washing with organic solvents such as ethanol, dioxane, and acetone. Since isocyanate groups are highly reactive and sensitive to water, this dyeing method cannot be performed in aqueous solutions.

Mishukova et al. used p-dimethylamino cinnamaldehyde as an example to dye spandex, with the reaction mechanism shown in Figure 11 [39].

Figure 11. Reaction Mechanism of p-Dimethylamino Cinnamaldehyde with Spandex

This method utilizes the aldehyde group to react with the amino groups on spandex fibers, forming colored Schiff base derivatives on the fibers to achieve color. The dyeing procedure is as follows: set spandex at 5 g, bath ratio of 1:20, aldehyde concentration from 0.1% to 3% (o.w.f.), pH < 2, and dyeing at 100°C for 45 minutes. The maximum wavelength of the reflectance curve of the dyed spandex is at 540 nm, and when the aldehyde concentration is 1%, the color depth of the dyed spandex reaches over 20.

7. Conclusion

The development of new dyeing methods based on chemical reactions requires a thorough consideration of both the characteristics of the chemical reactions and the fiber structure. The role of chemical reactions is mainly to form covalent bonds, thereby firmly attaching the dye chromophore to the fiber. Some chemical reactions can also form new conjugated systems (such as coupling reactions, Maillard reactions, etc.). These new dyeing methods, based on chemical reactions, offer new approaches for obtaining fibers with high color fastness. However, compared to existing dyeing methods, these new methods often still have unsatisfactory aspects in terms of effectiveness, efficiency, or cost. Additionally, some dyeing methods cause noticeable damage to the fibers, and these issues need to be addressed through further research to find appropriate solutions. Furthermore, as the concept of environmental sustainability gains importance, the development of new dyeing methods must take into account the impact of reagents and production waste on human health and the environment, while still meeting the high-quality demands of consumers.

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Research Progress in Dyeing Methods Based on Chemical Reactions

JI Zhengfang1,2 JIANG Hua3

( 1. Zhejiang Hongyi Chemical Co., Ltd., Lishui 323700, Zhejiang China; 2. Zhejiang Daoyuan New Mate-rials Co., Ltd., Lishui 323700, Zhejiang China; 3. Engineering Research Center for Eco-Dyeing and Finishing of Textiles, Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, Zhejiang China)

Abstract: Some new reactive dyeing methods developed in recent years based on chemical reactions were introduced, including diazo-tization-coupling reaction, diazotization-nucleophilic substitution reaction, Mannich reaction, Maillard reaction, carbene chemical re-actions, etc. The basic principles, dyeing processes, and dyeing performances of these dyeing methods were given. Their advantages and disadvantages were evaluated. The prospects of these reactive dyeing methods were discussed.

Keywords: reactive dyeing; coupling reaction; Mannich reaction; Maillard reaction; carbene insertion reaction

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