CN108342912B - Method for dyeing seaweed fibers with polycarboxylate dyes - Google Patents

Abstract

The invention belongs to the technical field of fiber dyeing, and particularly relates to a method for dyeing alginate fibers by using polycarboxylic acid type dye. The method for dyeing the alginate fiber by the polycarboxylic acid type dye takes metal ions as a connector, and the polycarboxylic acid type dye can form a complex bond with the alginate fiber and the polycarboxylic acid type dye to realize the dyeing of the polycarboxylic acid type dye on the alginate fiber; and adding the alginate fibers into the dye solution for dyeing, soap boiling, washing with water and drying in the air. The dyed alginate fiber has uniform color and bright color, and can completely meet the requirements of alginate fiber dyeing processing. In addition, the dyeing process disclosed by the invention has the characteristics of simplicity, convenience, mild condition and adoption of traditional dyeing equipment, and is very suitable for industrial application.

Description

Method for dyeing seaweed fibers with polycarboxylate dyes

technical field

The invention belongs to the technical field of fiber dyeing, in particular to a method for dyeing seaweed fibers with polycarboxylic acid type dyes.

Background technique

Seaweed fiber is a new type of biodegradable synthetic fiber, which is prepared by extracting sodium alginate from natural seaweed, purifying and processing, and then wet spinning. This type of fiber not only has the characteristics of moisture absorption, softness, heat preservation and biocompatibility of traditional natural fibers, but also has excellent flame retardant, antistatic and antibacterial properties, so it has a wide range of industrial application prospects.

Since the invention of seaweed fiber in 1944, although there have been many research and industrial development at home and abroad, its main uses are still concentrated in medical dressings, masks and other products in the field of non-textile clothing, and cannot be used in the field of textile and clothing. Type fibers are difficult to dye and finish. The structural characteristics of seaweed fibers make it very easy to exchange ions between fibers and solutions in solutions containing inorganic or organic sodium salts, so that the fibers gel or even dissolve completely in water. Inorganic or organic sodium salts are dyeing auxiliaries that must be added to traditional dyes in the dyeing process to achieve functions such as dye-promoting. Therefore, seaweed fibers have been unable to be dyed with traditional dye structures and cannot be industrialized. In order to accelerate the industrial application of seaweed fiber in the field of clothing, efforts to break through the bottleneck of seaweed fiber dyeing and processing has become a hot and difficult point of research.

The existing dyeing methods of seaweed fibers can be basically divided into four categories, namely, dope dyeing, fiber modification, direct dyeing of alginate fibers with existing reactive dyes, and dyeing of seaweed fibers with dyes containing polyamine skeleton structure. dyeing.

The first category is the method of coloring with the original solution. Chinese patent CN104264280A discloses a method for coloring seaweed fiber stock solution with lake dye. The method is to add sodium alginate into deionized water, stir to fully dissolve, prepare seaweed fiber spinning stock solution, and then spin seaweed fiber into seaweed fiber. The lake dye is added to the stock solution, and after stirring and mixing evenly, the lake dye-colored seaweed fiber spinning solution is obtained after filtration and defoaming, and the lake dye-colored seaweed fiber is further prepared. Wang Ping, et al. Chinese Journal of Textiles [J], Influence of fluorescent pigments on the properties of algal fiber spinning solution and its membrane, 2015, 05:48-53. It was reported that fluorescent pigments were used to color alginate fiber stock solution, and the research its film-forming properties.

The second category is the method of fiber modification. Chinese patent CN101736440A discloses a method for manufacturing dyeable alginate fibers. In the method, water-soluble dendritic macromolecular compounds are added to the spinning solution of alginate fibers, and wet spinning equipment and technology are used. stretching, washing and post-treatment to obtain alginate fibers with good dyeing properties.

The third category is the use of existing direct and reactive dyes to dye alginate fibers. Chinese patent CN101413207A discloses a dyeing and finishing process for seaweed fiber fabrics. The patent introduces the traditional dyeing process of directly using reactive dyes, and realizes the coloring of alginic acid fibers through the dyeing and color-fixing effects of sodium sulfate and soda ash. Kong Baoyun, et al. Dyeing process of seaweed fibers with reactive dyes [J], Printing and Dyeing, 2013, 08:22-24. It is reported that the use of calcium chloride instead of traditional sodium sulfate as a dye accelerator for dyeing alginate fibers with reactive dyes has a good effect on seaweed fibers. The acid fibers are dyed to avoid the damage of the algal fibers by sodium ions. Lv Fangbing, et al. Rare earth dyeing of seaweed fibers with reactive dyes [J], 2009, 24:11-14. Reported in the method that cerium nitrate was used instead of sodium sulfate, and the dyeing of alginate fibers was completed by using various types of reactive dyes. Chinese patent CN103981744A discloses a salt-free dyeing process for calcium alginate fibers. The patent first uses aluminum sulfate aqueous solution to pretreat calcium alginate fibers, then uses direct dyes for salt-free dyeing, and finally uses calcium chloride aqueous solution for color-fixing treatment , to dye calcium alginate fibers.

The fourth category is to dye seaweed fibers with dyes containing polyamine skeleton structure. Chinese patent CN105332291A discloses a method for dyeing calcium alginate fibers. This patent mainly uses dyes containing polyvinylpolyamine skeleton structure to make the dyes have cationic charges in a dyebath with a certain pH value, so as to realize dyes and negatively charged dyes. The calcium alginate fibers are adsorbed and fixed by ionic bonding. Sun Liang, Guo Yingjie, Xia Yanzhi, et al. Study on the use of polyamine dyes for calcium alginate fiber dyeing [J], Dyeing and Finishing Technology, 2017(6): 29-32. .Research on new dyes for alginate fibers [J], Wool Spinning Technology, 2017(8): 40-43. The use of this type of dyes to dye seaweed fibers was reported in the study of polyamine dyes for calcium alginate fiber dyeing process research.

The above-mentioned dyeing process for seaweed fiber has all made beneficial attempts, but there are still many problems. Especially in the dyeing process, there are still defects such as low coloring rate, few types of dyes, large loss of strength and complicated dyeing process. Based on this, the research on the efficient dyeing process for seaweed fibers is still a hot and difficult point of research.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a method for dyeing seaweed fibers with polycarboxylic acid type dyes with high dyeing rate, low strength loss and high soaping fastness.

The method for dyeing seaweed fibers with polycarboxylic acid type dyes of the present invention uses metal ions as connectors, and the metal ions can form complex bonds with seaweed fibers and polycarboxylic acid type dyes, so as to realize the effect of polycarboxylic acid type dyes on seaweed. Fiber dyeing.

The structural formula of the polycarboxylic acid type dye is:

Wherein: M is an alkali metal ion;

X is O or NH, directly connected to the aromatic ring chromophore group;

D is an aromatic ring chromophore group with an azo structure or an anthraquinone structure;

n ₁ =1-100, n ₂ =1-100, n=1-1000.

The method for dyeing seaweed fibers with polycarboxylic acid type dyes of the present invention comprises the following steps: dissolving the polycarboxylic acid type dyes in water, adjusting the pH value, adding inorganic metal salts to obtain a dye liquor; and then adding the seaweed fibers into the dye liquor Dyeing, soaping, washing and drying.

in:

The inorganic metal salt is one of sulfate, hydrochloride, nitrate or phosphate of copper, nickel, cadmium, iron, zinc, calcium, silver, chromium, and tin.

The mass ratio of inorganic metal salt to seaweed fiber is 0.1-5:100.

The mass ratio of polycarboxylate dye to seaweed fiber is 1-8:100.

The mass ratio of water to seaweed fibers is 10-50:1.

The pH value is adjusted to 3-8 by using a pH value adjuster, and the pH value adjuster is one of hydrochloric acid, ammonia water or sulfuric acid.

The dyeing temperature is 30-90℃, and the dyeing time is 30-80min.

Use 1-4‰ neutral soap solution for soap cooking, the soap cooking temperature is 90-95 ℃, and the soap cooking time is 10-15min.

The beneficial effects of the present invention are as follows:

The seaweed fiber structure of the invention contains a large number of carboxyl groups and hydroxyl groups, which can form metal complex bonds with metal ions. The polycarboxylic acid dyes containing a large number of carboxyl groups can also form metal complex bonds with metal ions. Thereby, metal ions are used as "bonds" to form metal complex bonds with seaweed fibers and polycarboxylate dyes, so as to realize the adsorption and fixation of polycarboxylate dyes to seaweed fibers.

The metal ions added in the dyeing process will not cause a large amount of loss of the original metal ions in the seaweed fiber, avoiding the damage to the strength of the seaweed fiber; and through a certain dyeing process and the selection of metal ions, the original strength performance of the seaweed fiber can also be improved . Compared with the hydrogen bonds and ionic bonds formed by the existing dyes and seaweed fibers, the metal complex bonds formed by the polycarboxylic acid type dyes and seaweed fibers are more stable and firmer, so that the dyed fibers can be given higher strength and better performance. Dyeing effect.

The dyed seaweed fibers of the invention have uniform color and bright color, and can fully meet the requirements of seaweed fiber dyeing and processing. In addition, the dyeing process of the present invention also has the characteristics of simplicity, convenience, mild conditions and the use of traditional dyeing equipment, which is very suitable for industrial application.

Detailed ways

The present invention will be further described below in conjunction with the embodiments.

Example 1

The method for dyeing seaweed fibers with polycarboxylic acid type dyes uses metal ions as connectors, and complex bonds can be formed through metal ions, seaweed fibers and polycarboxylic acid type dyes, so as to realize the effect of polycarboxylic acid type dyes on seaweed fibers. dyed. The structural formula of the polycarboxylic acid type dye DY-1 is:

where: n ₁ =10-15, n ₂ =10-15, n=80-100.

The method for dyeing seaweed fibers with described polycarboxylic acid type dyes is as follows:

Dissolve 0.5g of the polycarboxylic acid type dye in 400g of water, add 1% hydrochloric acid solution to adjust the pH value to 4.5, then add 0.3g of tin sulfate, and mix evenly to obtain a dye liquor; then add 30g of seaweed fibers to the dye liquor at 60°C Dyeing for 60min. After dyeing, take out the seaweed fiber, soak it in 4‰ neutral soap solution, and cook it at 95℃ for 10min. Finally, wash the seaweed fiber fully and air dry.

Example 2

The method for dyeing seaweed fibers with polycarboxylic acid type dyes uses metal ions as connectors, and complex bonds can be formed through metal ions, seaweed fibers and polycarboxylic acid type dyes, so as to realize the effect of polycarboxylic acid type dyes on seaweed fibers. dyed. Described polycarboxylic acid type dye DY-2 structural formula is:

Where: n ₁ =5-8, n ₂ =5-8, n=100-150.

The method for dyeing seaweed fibers with described polycarboxylic acid type dyes is as follows:

Dissolve 1.5g of the polycarboxylic acid type dye in 600g of water, add 1% ammonia solution to adjust the pH value to 6.5, then add 1g of chromium sulfate, and mix evenly to obtain a dye solution; then add 30g of seaweed fiber to the dye solution at 70°C Dyeing for 40min, after dyeing, take out the seaweed fiber, soak it in a neutral soap solution of 2‰, and cook it at 90℃ for 15min. Finally, the seaweed fiber is fully washed and air-dried.

Example 3

The method for dyeing seaweed fibers with polycarboxylic acid type dyes uses metal ions as connectors, and complex bonds can be formed through metal ions, seaweed fibers and polycarboxylic acid type dyes, so as to realize the effect of polycarboxylic acid type dyes on seaweed fibers. dyed. Described polycarboxylic acid type dye DY-3 structural formula is:

Wherein: n ₁ =20-25, n ₂ =20-25, n=400-500.

The method for dyeing seaweed fibers with described polycarboxylic acid type dyes is as follows:

Dissolve 2g of the polycarboxylic acid type dye in 500g of water, add 1% ammonia solution to adjust the pH value to 7.0, then add 1.2g of copper chloride, and mix evenly to obtain a dye liquor; then add 30g of seaweed fibers to the dye liquor at 80°C Dyeing for 50min. After dyeing, take out the seaweed fiber, soak it in 4‰ neutral soap solution, and cook it at 92℃ for 14min. Finally, wash the seaweed fiber fully and air dry.

Example 4

The method for dyeing seaweed fibers with polycarboxylic acid type dyes uses metal ions as connectors, and complex bonds can be formed through metal ions, seaweed fibers and polycarboxylic acid type dyes, so as to realize the effect of polycarboxylic acid type dyes on seaweed fibers. dyed. Described polycarboxylic acid type dye DY-4 structural formula is:

where: n ₁ =40-45, n ₂ =40-45, n=50-100.

The method for dyeing seaweed fibers with described polycarboxylic acid type dyes is as follows:

Dissolve 0.5g of the polycarboxylic acid type dye in 500g of water, add 1% sulfuric acid solution to adjust the pH value to 4.0, then add 1.5g of zinc nitrate, and mix evenly to obtain a dye solution; then add 30g of seaweed fiber to the dye solution at 50°C Dyeing for 70min. After dyeing, take out the seaweed fiber, soak it in 3‰ neutral soap solution, and cook it at 95℃ for 11min. Finally, wash the seaweed fiber fully and air dry.

Comparative Example 1

Example 1 in patent CN105332291A is taken as comparative example 1.

The dyed seaweed fibers obtained in Examples 1-4 and Comparative Example 1 were tested for dye uptake, strength properties, and soaping fastness, and the undyed seaweed fibers were tested for strength properties. The strength performance after dyeing is measured with reference to GB/T14337-2008; the soaping fastness is measured with reference to GB/T3921-2008; the dye uptake is measured by spectrophotometer before and after dyeing. . The specific measurement data are shown in Table 1.

Table 1 Test result table

Example breaking strength Strong rate of change Dyeing rate Soaping fastness Example 1 3.48cN/dtex 2.2% lower 81% level 4 Example 2 3.92cN/dtex 10.1% increase 86% level 4 Example 3 3.84cN/dtex 7.9% increase 79% level 4 Example 4 3.45N/dtex 3.1% lower 87% Level 3-4 Comparative Example 1 3.35N/dtex 5.9% lower 81% Level 3-4 Undyed seaweed fiber 3.56cN/dtex - - -

It is known from Table 1 that the dyeing rate of Comparative Example 1 is the same as that in Example 1. However, in Comparative Example 1, the dyes and calcium alginate fibers were adsorbed and fixed by ionic bonds, while in Example 1, the dyes and algae fibers were adsorbed and fixed by complex bonds. Due to the high strength of the complex bonds Due to the strength of the ionic bond, the fiber strength loss in Example 1 is smaller than that in Comparative Example 1.

The used dyestuff of the present invention is synthesized according to the following documents, and its synthetic method is the conventional method in this area:

(1) Xu Hua, Synthesis and application of polycarboxylic acid and polycarboxylate macromolecular dyes [D]. Dalian University of Technology, 2011.

(2) Tang Bingtao, Zhang Shufen, Ma Wei, Polycarboxylic acid dyes with low polymerization degree, CN101891968A[P].2010.

(3) Deng Yong, Synthesis and application of polymaleic acid (ester) macromolecular dyes [D]. Dalian University of Technology, 2013.

Claims (7)

1. a method for dyeing seaweed fibers with polycarboxylic acid type dyes, it is characterized in that: with metal ion as connector, all can form complex bond by metal ion and seaweed fiber, polycarboxylic acid type dye, realize polycarboxylic acid type Dyeing of seaweed fibers with dyes; The structural formula of the polycarboxylic acid type dye is:

Wherein: M is an alkali metal ion; X is O or NH; D is an aromatic ring chromophore group with an azo structure or an anthraquinone structure; n ₁ =1-100, n ₂ = 1-100, n=1-1000; The method for dyeing seaweed fibers with the polycarboxylic acid type dye: dissolving the polycarboxylic acid type dye in water, adjusting the pH value, adding inorganic metal salts to obtain a dye liquor; then adding the seaweed fibers into the dye liquor for dyeing, and soaping , washed and dried; The inorganic metal salt is one of sulfate, hydrochloride, nitrate or phosphate of copper, nickel, cadmium, iron, zinc, calcium, silver, chromium, and tin. 2. The method for dyeing seaweed fibers with polycarboxylic acid type dyes according to claim 1, wherein the mass ratio of inorganic metal salt and seaweed fibers is 0.1-5:100. 3. the method for dyeing seaweed fiber with polycarboxylic acid type dye according to claim 1, is characterized in that: the mass ratio of polycarboxylic acid type dye and seaweed fiber is 1-8:100. 4. the method for dyeing seaweed fiber with polycarboxylic acid type dye according to claim 1, is characterized in that: when dyeing, the mass ratio of water and seaweed fiber is 10-50:1. 5. the method for dyeing seaweed fiber with polycarboxylic acid type dye according to claim 1, is characterized in that: adopting pH value adjusting agent to regulate pH value is 3-8, and described pH value adjusting agent is hydrochloric acid, ammoniacal liquor or sulfuric acid one of the. 6 . The method for dyeing seaweed fibers with polycarboxylic acid type dyes according to claim 1 , wherein the dyeing temperature is 30-90° C. and the dyeing time is 30-80 min. 7 . 7. the method for dyeing seaweed fiber with polycarboxylic acid type dyes according to claim 1, is characterized in that: adopt the neutral soap solution of 1-4‰ to carry out soap boiling, soap boiling temperature is 90-95 ℃, and soap boiling time for 10-15min.