CN108774908A - A kind of cationic dye capable of dyeing nylon 6 fiber - Google Patents

Abstract

The invention relates to a cationic dye-dyeable nylon 6 fiber, which belongs to a preparation method of a novel differential fiber. By surface treatment of nylon 6 fiber, the pollution and impurities attached to the surface are removed; at room temperature or at a lower temperature close to room temperature, the nylon 6 fiber is catalyzed by an initiator in water, and the nylon 6 fiber is grafted and polymerized with acrylic acid to make the nylon 6 fiber The surface is grafted with polyacrylic acid, and the carboxyl group is introduced into the surface of nylon 6 fiber. Through the combination of carboxyl and cationic active sites in cationic dyes, the dye uptake rate of cationic dyes can be improved. This method avoids the high-temperature synthesis process, and through short-time treatment, the nylon 6 fiber can obtain the dyeing ability of cationic dyes, the method is simple and easy, and it is energy-saving and environment-friendly.

Description

A kind of cationic dye can dye nylon 6 fiber

technical field

The invention relates to a cationic dye-dyeable nylon 6 fiber, which belongs to a preparation method of a novel differential fiber.

Background technique

Nylon 6 is one of the main varieties of polyamide fibers, also known as polyamide 6, is one of the most important synthetic fibers and is widely used in the production of various clothing fabrics. With the increase of people's requirements for clothing fabrics, the shortcomings of ordinary nylon 6 in dyeability, antistatic, hygroscopicity, heat resistance and other properties are becoming more and more obvious. Cationic dye-dyeable nylon 6 fibers have been developed abroad, and have been widely used in textiles such as carpets and curtains. The principle is to introduce some functional groups that can be compatible with cationic dyes to the nylon 6 polymer chain that has only anionic dye affinity points - amino groups. The general method is to copolymerize caprolactam and monomers with sulfonic acid groups to obtain polyamide 6 polymer chains with sulfonic acid side groups. This method requires high-temperature polymerization from monomers, requiring some modifications to the production line. For large-scale production lines with small market demand and relatively fixed production equipment, the transformation cost is high, process adjustment is difficult, and it is difficult to realize industrialization. It is relatively simple and easy to only carry out surface treatment on the nylon 6 fiber to make the surface slightly grafted and obtain some groups that are compatible with cationic dyes. The present invention introduces anionic groups into the surface of nylon 6 fibers through the graft polymerization reaction of acrylic acid on nylon 6 at 0-40°C under relatively mild reaction conditions in a short period of time, so that the fibers have the ability to be dyed by cationic dyes. ability. Exhibits better dyeing ability, and achieves more vivid colors and antistatic ability. This method avoids tedious steps such as high-temperature synthesis, and monomer removal and recovery after synthesis. The operation temperature is low, the time is short, and the by-product polyacrylic acid is easy to recover, which belongs to the green production process.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies in the prior art, prepare a kind of cationic dye can dye nylon 6 fiber.

Technical scheme of the present invention is summarized as follows:

A cationic dye can dye nylon 6 fiber, which is characterized in that nylon 6 fiber is surface-treated to remove pollution and impurities attached to the surface; at a temperature of 0-40°C, it is catalyzed by an initiator in water to make nylon 6 fiber and acrylic acid Carrying out graft polymerization, grafting polyacrylic acid on the surface of nylon 6 fiber, and introducing carboxyl group into the surface of nylon 6 fiber. The nylon 6 fiber is combined with the cationic active site in the cationic dye through the carboxyl group to increase the dye uptake rate of the cationic dye.

The surface treatment process is: (1) nylon 6 fiber is ultrasonically cleaned with deionized water; (2) nylon 6 fiber is ultrasonically cleaned with absolute ethanol; (3) nylon 6 fiber is rinsed with deionized water and absolute ethanol; the steps ( Combination of one and/or multiple repetitions of 1), (2) and (3).

The initiator is one of the three groups of oxidation-reduction initiators: H ₂ O ₂ -Na ₂ SO ₃ or H ₂ O ₂ -Cu ₂ Cl ₂ or Na ₂ S ₂ O ₈ -Na ₂ SO ₃ ; oxidizing and reducing agents The molar ratio is (1.1～2.5):1.

The mass concentration of acrylic acid in the reaction system is 5wt%-30wt%; the reaction time is 10-120 minutes.

Description of drawings

Fig. 1 is the photo of ungrafted nylon 6 fiber after methylene blue dyeing; Fig. 2 is the photo of the grafted nylon 6 fiber prepared by embodiment 1 after methylene blue dyeing; Fig. 3 is the grafted nylon 6 fiber prepared by embodiment 3 Photographs after methylene blue staining.

Example

Preparation Example of Cationic Dyes Dyeable Nylon 6 Fiber

Example 1

Put 1g of nylon 6 fiber in deionized water and ultrasonically clean it for 30min; then put it in absolute ethanol for ultrasonic cleaning for 30min, then rinse it with absolute ethanol for 3 times; in the bottle. Weigh 0.8g of Na ₂ SO ₃ powder into the conical flask, add 75mL of water, and then add 1.2mL of 30wt% H ₂ O ₂ . Place the Erlenmeyer flask in a constant temperature shaker and shake at 30°C for 30min. Add 15mL of acrylic acid dropwise to the Erlenmeyer flask, add water until the total volume of the liquid is 100mL, and react for 90min. The nylon 6 fibers after the reaction were ultrasonically washed for 15 minutes, rinsed repeatedly with deionized water, and waited to be dyed.

Example 2

Weigh 0.5g of nylon 6 fiber into a 250mL Erlenmeyer flask, add deionized water, and ultrasonically clean for 30min; discard the water and rinse with fresh deionized water for 3 times. Add absolute ethanol, ultrasonically clean for 30 minutes, then rinse with absolute ethanol 3 times; finally rinse with deionized water. Add 2.58g Cu ₂ Cl ₂ , 85mL deionized water, heat to 30°C in a constant temperature shaker, add 1mL 30wt% H ₂ O ₂ , pre-oxidize for 30min, add 10mL acrylic acid, and shake at constant temperature for 60min. The reaction liquid was filtered off, and 100 mL of 0.1 M hydrochloric acid was added, and the mixture was shaken for 10 min. Take out the fiber, wash it with deionized water until neutral, put it in 50mL deionized water and vibrate ultrasonically for 10min twice, rinse with deionized water, and wait for dyeing.

Example 3

1 g of nylon 6 fiber was placed in deionized water, ultrasonically cleaned for 30 min, then ultrasonically cleaned with absolute ethanol for 30 min, rinsed with absolute ethanol and deionized water for 3 times, and placed in a 250 mL ground-mouth Erlenmeyer flask. Weigh 0.8g of Na ₂ SO ₃ powder into a conical flask, add 75mL of water, and shake at a constant temperature of 15°C. 2.5g Na ₂ S ₂ O ₈ was prepared into 10mL aqueous solution, added dropwise into the Erlenmeyer flask, and shaken for 30min. Add 20mL of acrylic acid dropwise to the bottle, add water until the total volume of the liquid is 120mL, and react for 30min. Take out the nylon 6 fiber, rinse it repeatedly with deionized water, and wait for dyeing.

Example 4

1 g of nylon 6 fiber was ultrasonically cleaned with deionized water for 30 min, and then ultrasonically cleaned in absolute ethanol for 30 min. After rinsing with absolute ethanol for 3 times, rinse with deionized water, and place in a 250mL ground-mouth Erlenmeyer flask. Weigh 0.6g of Na ₂ SO ₃ powder into the Erlenmeyer flask, add 70mL of water, and vibrate at a constant temperature of 0°C. 1.5g Na ₂ S ₂ O ₈ was prepared into 15mL aqueous solution, added dropwise to the Erlenmeyer flask, and shaken for 40min. Add 30mL of acrylic acid dropwise to the bottle, adjust the total volume of the liquid in the bottle to 150mL, and react for 120min. Take out the nylon 6 fiber, rinse it repeatedly with deionized water, and wait for dyeing.

Example 5

Weigh 2g of nylon 6 fiber and place it in a 250mL Erlenmeyer flask, ultrasonically clean it with deionized water for 30min, and then rinse it with deionized water for 3 times. Ultrasonic cleaning with absolute ethanol for 30 minutes, then rinsed with absolute ethanol for 3 times; finally rinsed with deionized water. Add 3.87g Cu ₂ Cl ₂ , 90mL deionized water, place in a constant temperature oscillator and heat to 40°C, add 3mL of 30wt% H ₂ O ₂ , shake for 10min, then add 5mL of acrylic acid, shake for 20min at constant temperature. The reaction solution was filtered off, 100mL of 0.1M hydrochloric acid was added, and shaken for 10min. Take out the fiber, wash it with deionized water until neutral, and wait for dyeing.

Example 6

0.8 g of nylon 6 fibers were ultrasonically cleaned with deionized water for 30 min, followed by ultrasonic cleaning with absolute ethanol for 30 min. Finally, rinse with absolute ethanol and deionized water three times alternately. Placed in a 250mL ground-mouth Erlenmeyer flask. Measure 1.2g of Na ₂ SO ₃ powder into the conical flask, add 70mL of water, and then add 0.8mL of 30wt% H ₂ O ₂ . Place the Erlenmeyer flask in a constant temperature shaker at 35°C and shake for 30min. Add 25mL of acrylic acid dropwise to the Erlenmeyer flask, add deionized water to make it 100mL, and react for 40min. Take out the nylon 6 fiber, put it in water for ultrasonic cleaning for 15 minutes, rinse it repeatedly with deionized water, and wait for dyeing.

Dyeing example

Example 7

Prepare a methylene blue dyeing solution with a concentration of 1 g/L, weigh 1 g of grafted nylon 6 fiber and place it in a ground-mouth Erlenmeyer flask, add 200 mL of methylene blue aqueous solution to make the bath ratio 1:200. Place in a water bath at 30°C for initial dyeing, heat up to 95°C at 1°C/min, keep warm for 1 hour and take it out. Rinse repeatedly with deionized water until the water is colorless, place the fiber in a constant temperature drying oven, and dry at 60°C.

Claims (4)

1. A kind of cationic dye can dye nylon 6 fiber, it is characterized in that by carrying out surface treatment to nylon 6 fiber to remove the pollution and the impurity attached to the surface, then in water, temperature is under 0～40 ℃, under initiator catalysis and acrylic acid Carry out graft polymerization, make nylon 6 fiber surface graft polyacrylic acid, introduce carboxyl group into nylon 6 fiber surface, make nylon 6 fiber combine with cationic active site in cationic dye through carboxyl group, improve the dyeing rate of cationic dye. 2. according to claim 1, described surface treatment is: (1) nylon 6 fiber is ultrasonically cleaned with deionized water; (2) nylon 6 fiber is cleaned with deionized water ultrasonically; (3) nylon 6 fiber is cleaned with deionized water Rinse with absolute ethanol; step (1) (2) and (3) one and/or the combination of repeated operations. 3. According to claim 1, said initiator is H ₂ O ₂ -Na ₂ SO ₃ or H ₂ O ₂ -Cu ₂ Cl ₂ or Na ₂ S ₂ O ₈ -Na ₂ SO ₃ three groups of oxidation-reduction initiation A group of agents; the molar ratio of oxidizing agent to reducing agent is (1.1-2.5):1. 4. According to claim 1, the mass concentration of the acrylic acid in the reaction system is 5wt%-30wt%; the reaction time is 10-120 minutes.