CN114645474B

CN114645474B - Application of dye based on polyphenol amine in printing and dyeing fabric fiber and dyeing method

Info

Publication number: CN114645474B
Application number: CN202210438525.8A
Authority: CN
Inventors: 高婷婷; 李丰华; 周国伟; 刘钦泽
Original assignee: Qilu University of Technology
Current assignee: Qilu University of Technology
Priority date: 2022-04-25
Filing date: 2022-04-25
Publication date: 2023-05-09
Anticipated expiration: 2042-04-25
Also published as: CN114645474A

Abstract

The invention belongs to the technical field of textile printing and dyeing, and relates to an application of a polyaniline-based dye in printing and dyeing textile fibers and a dyeing method. The polyethyleneimine and catechol are subjected to oxidative polymerization reaction in water in the presence of oxygen to obtain a polyphenol amine dye, and the fabric fiber is added into the polyphenol amine dye for dyeing. The dyeing based on the polyphenol amine dye can omit a printing and dyeing auxiliary agent, reduce the use amount of fresh water, improve the color fastness and enable the printed and dyed material to have antibacterial performance.

Description

Application of dye based on polyphenol amine in printing and dyeing fabric fiber and dyeing method

Technical Field

The invention belongs to the technical field of textile printing and dyeing, and relates to an application of a polyaniline-based dye in printing and dyeing textile fibers and a dyeing method.

Background

The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.

The traditional dye has low color fastness, so that washing color fading or color cross phenomenon is caused. In addition, a large amount of printing auxiliary agents and fresh water are used in the traditional fiber printing and dyeing process, so that the production cost and the process complexity are increased, the printing and dyeing wastewater is always high in salt and alkalinity and is difficult to treat, and great difficulty is brought to environmental treatment. To solve this problem, the present solution has been studied and known by the inventors, including cationic modification of fibers, dyeing with a nonaqueous medium, dyeing with polymer nanospheres, and supercritical carbon dioxide dyeing. Although the methods can reduce the use of auxiliary agents in the dyeing process, reduce the consumption of water resources, improve the dye-uptake of the dye, improve the color fastness and the like. However, it is difficult to realize a real industrial application because of problems such as increased dyeing process, more energy consumption, increased dyeing cost, safety of required equipment, and environmental hazard of reagents.

Disclosure of Invention

In order to solve the defects in the prior art, the invention aims to provide an application of a polyaniline dye-based dyeing method in dyeing textile fibers, and the application of the polyaniline dye-based dyeing method can omit a dyeing auxiliary agent, reduce the use amount of fresh water, improve color fastness and enable the dyed material to have antibacterial performance.

In order to achieve the above purpose, the technical scheme of the invention is as follows:

in one aspect, the application of the polyphenol amine-based dye in printing and dyeing textile fibers is characterized in that the preparation method of the polyphenol amine-based dye comprises the following steps: the polyethyleneimine and catechol are obtained by oxidation polymerization reaction in water in the presence of oxygen.

In another aspect, a dyeing method comprises performing oxidative polymerization of polyethyleneimine and catechol in water in the presence of oxygen to obtain a polyphenol amine dye, and adding fabric fibers into the polyphenol amine dye for dyeing.

Research shows that catechol is oxidized into o-phthalquinone, then Schiff base reaction and Michael addition reaction are carried out on the o-phthalquinone and amine groups of polyethyleneimine to generate stable Schiff base structure and rearranged 4-or 6-position monosubstituted catechol, the reaction is repeated continuously, and finally the phenolamine polymer, namely the polyphenylamine, is obtained. According to the invention, catecholamine prepared from polyethylenimine and catechol serving as raw materials can be modified on the surface of fabric fibers, and different colors can be generated by adjusting the proportion of polyethylenimine to catechol and the time. And the formed catecholamine has strong binding force with the fabric fiber, so that the dyeing temperature is mild, the dyeing speed is high, the color fastness is higher, the subsequent treatment step is not needed, and meanwhile, the dyed fabric fiber has certain antibacterial property.

In the third aspect, a method for utilizing a post-dyeing dye liquor, wherein the post-dyeing dye liquor is used as a recovery dye, and the fabric fiber is added into the recovery dye for dyeing; and the dyed dye liquor is the residual liquid material dyed according to the dyeing method.

Compared with the prior art, the invention has the following advantages and beneficial effects:

the fiber dyeing method provided by the invention can realize 20-minute rapid dyeing at low temperature without adding any process auxiliary agent, and has the advantages of low preparation cost, simple process and environmental protection;

the invention provides a method for dyeing 4 pieces of cotton fiber, mulberry silk and polyester fiber with the size of 5 multiplied by 10cm by using catecholamine as 200mL of dye, wherein the dyed dye liquor can be reused for a plurality of times;

the invention provides a method for dyeing cotton fiber, mulberry silk and polyester fiber by using catecholamine as dye, wherein different colors of fabrics can be realized by regulating the proportion of phenol and amine and the dyeing time. Under the condition of low temperature of 35 ℃ and no addition of any process auxiliary agent, the rapid dyeing for 20 minutes can be realized. The dye liquor has good reusability and antibacterial property. The cotton fiber and the polyester fiber can be circularly dyed for 8 times, and the mulberry silk can be circularly dyed for 5 times. In addition, the dyed fabrics have good washing color fastness, rubbing color fastness and perspiration color fastness. The catecholamine polymer dye has potential market application value by comprehensively considering the dyeing process, the material structural property and the dyeing effect.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.

FIG. 1 is an SEM image of pretreated textile fibers obtained in examples 1-3 of the invention, a being example 1, b being example 2, and c being example 3;

FIG. 2 is an SEM image of the fabric fibers dyed with catecholamine dye liquor obtained in examples 1 to 3 of the invention, a being example 1, b being example 2, c being example 3;

FIG. 3 is a graph showing the color development of three fabric fibers at different phenolic amine ratios in application example 1 of the present invention;

FIG. 4 is a bar graph showing the antibacterial effect of three dyed fabrics on E.coli and Staphylococcus aureus, as measured in application example 4 of the present invention.

Detailed Description

It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.

In view of the problems of a large amount of printing auxiliary agents and fresh water used in the traditional printing and dyeing process, the invention provides an application of a polyaniline dye in printing and dyeing textile fibers and a dyeing method in order to solve the problems of increased dyeing process, more energy consumption, increased printing and dyeing cost and the like in the prior art.

In an exemplary embodiment of the present invention, there is provided an application of a polyphenol amine dye in printing and dyeing textile fibers, wherein the preparation method based on the polyphenol amine dye comprises the following steps: the polyethyleneimine and catechol are obtained by oxidation polymerization reaction in water in the presence of oxygen. The water is fresh water such as river water, lake water and the like, and can be treated to obtain tap water, mineral water, purified water, distilled water, deionized water and the like. In order to avoid that other impurities in the water affect the dyeing effect, in some examples of this embodiment, the water is deionized water.

In some examples of this embodiment, the molar ratio of polyethyleneimine to catechol is from 1:1 to 17:1. ensuring complete reaction of the polyethyleneimine and thus making the fabric darker.

In some examples of this embodiment, the temperature of the reaction of the polyphenylamine is 25 to 45℃and the reaction time is 15 to 30 hours. This condition enables the reaction to be completed, ensuring the color intensity (K/S value) and the color fastness of the dyed fabric fibers.

In some examples of this embodiment, the fabric fibers are exemplified by cotton fibers, mulberry silk, or polyester fibers. The dye based on the polyphenol amine has universality for various fibers and has better dyeing effect for the mulberry silk of the three textile fibers. In addition, the research shows that when the fabric fiber is mulberry silk, the obtained dyed fabric fiber has better sterilization effect.

In another embodiment of the present invention, there is provided a dyeing method, in which polyethyleneimine and catechol are subjected to oxidative polymerization in water in the presence of oxygen to obtain a dye, and fabric fibers are dyed by adding the dye to the dye based on the polyphenol amine.

In some examples of this embodiment, the fabric fibers are subjected to a wash pretreatment prior to dyeing. Specifically, when the fabric fiber is cotton fiber, the cotton fiber is added into deionized water for washing, and drying is performed after washing. When the fabric fiber is mulberry silk or polyester fiber, the mulberry silk or polyester fiber is added into sodium carbonate solution for washing, and drying is carried out after washing. Wherein, the concentration of the sodium carbonate solution is preferably 0.1-0.6M. When in drying, the mulberry silk is dried at room temperature, and the dyeing effect is better. The drying temperature of the cotton fiber or the polyester fiber is 60-80 ℃.

In one or more embodiments, the wash pretreatment bath ratio is 1:45-55 (o.w.f.). The washing time is 10-50 min.

In some examples of this embodiment, the dyeing mode is a reciprocating oscillation at a speed of 100 to 200r/min.

In some examples of this embodiment, after dyeing, the fabric fibers are dried after being extracted from the dyed material. The drying mode is the same as that after the fabric fiber is washed and pretreated.

In a third embodiment of the present invention, a method for using a post-dyeing dye liquor is provided, wherein the post-dyeing dye liquor is used as a recovery dye, and a fabric fiber is dyed by adding the recovery dye; and the dyed dye liquor is the residual liquid material dyed according to the dyeing method.

Specifically, the dyeing mode is reciprocating oscillation, and the oscillation speed is 100-200 r/min.

Specifically, the dyed dye liquor produced by the method for utilizing the dyed dye liquor can still be further treated by adopting the method for utilizing the dyed dye liquor.

In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail below with reference to specific examples and comparative examples.

In the following examples, the cotton fiber is CC (CC cotton, drawing frame cotton), the mulberry silk is MS for short, and the polyester fiber is PET (polyethylene terephthalate).

Example 1

A method of dyeing cotton fibers with a novel dye produced by polymerization of catechol and polyethylenimine, comprising the steps of:

(1) Cotton fibers were treated at a bath ratio of 1:50 (o.w.f.) was added to deionized water for washing for 30min. After washing, after drying at 60 ℃ for 2 hours, pretreated textile fibers were obtained, as shown in fig. 1 a.

(2) 4 pieces of pretreated textile fibers having a size of 5X 10cm were taken, added to 200mL of a polyaniline dye solution containing 5.05mL of polyethylenimine and 1g of catechol polymerized at 35℃for 24 hours, and dyed at 35℃for 20 minutes. After thorough washing with deionized water, drying at 60 ℃ for 2 hours, the dyed fabric fiber is obtained, as shown in fig. 2 a.

Example 2

A method for dyeing mulberry silk with a novel dye produced by polymerization of catechol and polyethyleneimine, comprising the following steps:

(1) Mulberry silk is treated with bath ratio of 1:50 (o.w.f.) was added to a 0.3g/L sodium carbonate solution for washing for 30min. After washing, after drying at room temperature for 2 hours, pretreated textile fibers were obtained, as shown in fig. 1 b.

(2) 4 pieces of pretreated textile fibers having a size of 5X 10cm were taken, added to 200mL of a polyaniline dye solution containing 5.05mL of polyethylenimine and 1g of catechol polymerized at 35℃for 24 hours, and dyed at 35℃for 20 minutes. After thorough washing with deionized water, drying at room temperature for 2 hours, the dyed fabric fiber is obtained, as shown in fig. 2 b.

Example 3

A method for dyeing polyester fibers with novel dyes produced by polymerization of catechol and polyethylenimine, comprising the steps of:

(1) Polyester fiber was treated in a bath ratio of 1:50 (o.w.f.) was added to a 0.3g/L sodium carbonate solution for washing for 30min. After washing, after drying at 60 ℃ for 2 hours, pretreated textile fibers were obtained, as shown in fig. 1 c.

(2) 4 pieces of pretreated textile fibers having a size of 5X 10cm were taken, added to 200mL of a polyaniline dye solution containing 5.05mL of polyethylenimine and 1g of catechol polymerized at 35℃for 24 hours, and dyed at 35℃for 20 minutes. After washing with deionized water sufficiently, the polyester fiber was dried at 60 ℃ for 2 hours to obtain a dyed fabric fiber, as shown in fig. 2 c.

Example 4

(1) Cotton fibers were treated at a bath ratio of 1:50 (o.w.f.) was added to deionized water for washing for 30min. After washing, the pretreated textile fibers were obtained after drying at 60 ℃ for 2 hours.

(2) 4 pieces of pretreated textile fibers having a size of 5X 10cm were taken, added to 200mL of a polyaniline dye solution containing 1.26mL of polyethyleneimine and 1g of catechol polymerized at 35℃for 24 hours, and dyed at 35℃for 20 minutes. And (3) fully washing with deionized water, and drying at 60 ℃ for 2 hours to obtain the dyed fabric fiber.

Example 5

(1) Mulberry silk is treated with bath ratio of 1:50 (o.w.f.) was added to a 0.3g/L sodium carbonate solution for washing for 30min. After washing, the pretreated textile fibers were obtained after drying at room temperature for 2 hours.

(2) 4 pieces of pretreated textile fibers having a size of 5X 10cm were taken, added to 200mL of a polyaniline dye solution containing 1.26mL of polyethyleneimine and 1g of catechol polymerized at 35℃for 24 hours, and dyed at 35℃for 20 minutes. And (3) fully washing with deionized water, and drying at room temperature for 2 hours to obtain the dyed fabric fiber.

Example 6

(1) Polyester fiber was treated in a bath ratio of 1:50 (o.w.f.) was added to a 0.3g/L sodium carbonate solution for washing for 30min. After washing, the pretreated textile fibers were obtained after drying at 60 ℃ for 2 hours.

(2) 4 pieces of pretreated textile fibers having a size of 5X 10cm were taken, added to 200mL of a polyaniline dye solution containing 1.26mL of polyethyleneimine and 1g of catechol polymerized at 35℃for 24 hours, and dyed at 35℃for 20 minutes. And (3) fully washing the polyester fiber with deionized water, and drying the polyester fiber at 60 ℃ for 2 hours to obtain the dyed fabric fiber.

Example 7

(2) 4 pieces of pretreated textile fibers having a size of 5X 10cm were taken, added to 200mL of a polyaniline dye solution containing 0.51mL of polyethylenimine and 1g of catechol polymerized at 35℃for 24 hours, and dyed at 35℃for 20 minutes. And (3) fully washing with deionized water, and drying at 60 ℃ for 2 hours to obtain the dyed fabric fiber.

Example 8

(2) 4 pieces of pretreated textile fibers having a size of 5X 10cm were taken, added to 200mL of a polyaniline dye solution containing 0.51mL of polyethylenimine and 1g of catechol polymerized at 35℃for 24 hours, and dyed at 35℃for 20 minutes. And (3) fully washing with deionized water, and drying at room temperature for 2 hours to obtain the dyed fabric fiber.

Example 9

(2) 4 pieces of pretreated textile fibers having a size of 5X 10cm were taken, added to 200mL of a polyaniline dye solution containing 0.51mL of polyethylenimine and 1g of catechol polymerized at 35℃for 24 hours, and dyed at 35℃for 20 minutes. And (3) fully washing the polyester fiber with deionized water, and drying the polyester fiber at 60 ℃ for 2 hours to obtain the dyed fabric fiber.

Example 10

(2) 4 pieces of pretreated textile fibers having a size of 5X 10cm were taken, added to 200mL of a polyaniline dye solution containing 0.30mL of polyethyleneimine and 1g of catechol polymerized at 35℃for 24 hours, and dyed at 35℃for 20 minutes. And (3) fully washing with deionized water, and drying at 60 ℃ for 2 hours to obtain the dyed fabric fiber.

Example 11

(2) 4 pieces of pretreated textile fibers having a size of 5X 10cm were taken, added to 200mL of a polyaniline dye solution containing 0.30mL of polyethyleneimine and 1g of catechol polymerized at 35℃for 24 hours, and dyed at 35℃for 20 minutes. And (3) fully washing with deionized water, and drying at room temperature for 2 hours to obtain the dyed fabric fiber.

Example 12

(2) 4 pieces of pretreated textile fibers having a size of 5X 10cm were taken, added to 200mL of a polyaniline dye solution containing 0.30mL of polyethyleneimine and 1g of catechol polymerized at 35℃for 24 hours, and dyed at 35℃for 20 minutes. And (3) fully washing the polyester fiber with deionized water, and drying the polyester fiber at 60 ℃ for 2 hours to obtain the dyed fabric fiber.

Application example 1:

dyeing performance test of the polyphenylamine dye on three textile fibers at different phenolic amine molar ratios: the dyed fabric fibers obtained in examples 1 to 12 after dyeing were measured for reflectance of the fabric at a wavelength of 483nm using an ultraviolet spectrophotometer to calculate the color rendering index. The results are shown in FIG. 3, and FIG. 3 shows that the color rendering degree of mulberry silk is highest at each ratio.

Application example 2:

color fastness testing of the polyphenylamine dye to three textile fibers at a phenolamine mole ratio of 10:1 (i.e., examples 7, 8, 9): the washing fastness, rubbing fastness and perspiration fastness of the dyed fabrics were tested according to GB/T3921-2008A (1), GB/T3920-2008, GB/T3922-2013 and GB/T8427-2019, respectively. The test results are shown in Table 1.

TABLE 1 color fastness test results

The above table test results were issued by the Qingdao vison detection Co. Wherein, the grade 3 is qualified, more than 3 grades are good, and the grade 5 is excellent.

As can be seen from Table 1, the three fabrics dyed by the polyaniline dye of the present example all have acceptable and superior levels of wash fastness, rubbing fastness and perspiration fastness, and meet the requirements of textiles. This is because the polyphenol amine dye contains abundant catechol and primary amine groups, which can give excellent adhesiveness to the phenolic amine polymer, and thus can adhere to the surfaces of various fabrics, and has good color fastness.

Application example 3:

cyclic dyeing properties of the polyphenylamine dye on three textile fibers at a phenolamine mole ratio of 10:1: cotton fiber, mulberry silk and polyester fiber are respectively added into dye liquor with the phenolic amine molar ratio of 10:1, and the dye liquor is reused without supplementing dye. The time of cyclic dyeing is 20min, and the dyeing temperature is 35 ℃. The reflectivities of the three fabrics after each dyeing were measured separately and the corresponding K/S values calculated. The test results are shown in Table 2.

TABLE 2 results of the circulation dyeing properties of the Polyphenol amine dye solutions

As can be seen from Table 2, the K/S values of the fabrics are slightly reduced but the changes are not large after the mulberry silk is circularly dyed for 5 times and the cotton fiber and the polyester fiber are circularly dyed for 8 times, which shows that the polyaniline dye liquor has very good recycling property.

Application example 4:

antibacterial performance test of the polyphenylamine dye on three textile fibers at a phenolamine molar ratio of 10:1: the bacteria co-culture dilution plating technique is adopted. The two test strains were E.coli and Staphylococcus aureus, respectively. Sterilizing the fabric with ethylene oxide before testing, and placing small pieces of fabric (1×1 cm) into a concentration of 1×10 ⁸ Is allowed to stand at 37℃for 24 hours. Gradient dilutionAfter release, 100. Mu.L was plated onto nutrient agar. After the antibacterial test was completed, the bacterial colony count was evaluated by using a turbidimeter, and the test was repeated three times to calculate the bacterial reduction. The results are shown in fig. 4, and fig. 4 shows that the mulberry silk has the best antibacterial effect on two bacteria.

The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A dyeing method is characterized in that polyethyleneimine and catechol are subjected to oxidation polymerization reaction in water in the presence of oxygen to obtain a polyphenol amine dye, and fabric fibers are added into the polyphenol amine dye for dyeing.

2. A method of dyeing according to claim 1, wherein the water is deionized water.

3. A dyeing process according to claim 1, characterized in that the molar ratio of polyethylenimine to catechol is between 1:1 and 17:1;

or the reaction temperature of the polyaniline is 25-45 ℃ and the reaction time is 15-30 h.

4. A dyeing method according to claim 1, characterized in that the textile fibres are cotton fibres, mulberry silk or polyester fibres.

5. Dyeing process according to claim 1, characterized in that the textile fibres are subjected to a washing pretreatment before dyeing.

6. Dyeing process according to claim 5, characterized in that the bath ratio of the washing pretreatment is between 1:45 and 55o.w.f.; the washing time is 10-50 min.

7. The dyeing method according to claim 1, wherein the dyeing mode is reciprocating oscillation at a speed of 100-200 r/min.

8. Dyeing process according to claim 1, characterized in that after dyeing, the textile fibres are extracted from the dyed mass and dried.

9. The method for utilizing the dyed dye liquor is characterized in that the dyed dye liquor is used as a recovered dye, and the fabric fiber is added into the recovered dye for dyeing; the dyeing solution is the residual liquid material after dyeing according to the dyeing method of any one of claims 1-8.

10. The method for utilizing a post-dyeing dye solution according to claim 9, wherein the dyeing mode is reciprocating oscillation, and the oscillation speed is 100-200 r/min.