CN102911525A - Black reactive dye for dyeing nylon and preparation method thereof - Google Patents

Abstract

The invention relates to a black reactive dye for dyeing nylon and a preparation method thereof, wherein the preparation method comprises the steps of 1) quickly pouring 2-naphthol solution to 6-nitro-1, 2, 4-acid oxide solution to perform coupling to obtain a 1#base product; 2) enabling formic acid and chromium trioxide to react to obtain a chromizing agent; 3) enabling the 1#base and the chromizing agent to react to obtain a 1: 1 complex product; 4) quickly adding J acid solution to 6-nitro-1, 2, 4-acid oxide solution to obtain a 2#base product; 5) pouring the 1: 1 complex product to the 2#base product to obtain a 1: 2 complex product; 6) dropping the para-ester solution to cyanuric chloride to obtain a first condensation product; 7) adding the first condensation product to the 1: 2 complex product to obtain a second condensation product; and 8) hydrolyzing the product, obtaining a dye solution. The black reactive dye has bluish green coloured light and high solubility and does not increase environment pollution.

Description

A kind of black and active dye that is applicable to dyeing nylon and preparation method thereof

Technical field

The present invention relates to the reactive dyestuffs field, especially a kind of black and active dye that is applicable to dyeing nylon and preparation method thereof.

Background technology

Now the general nylon used dyestuff that dyes is matching stain, weak acid dye and metallized dye.Along with the exploitation of reactive dyestuffs application performance, the dyeing of reactive dyestuffs has spreaded all over the dyeing of the fabrics such as cotton, hair, nylon, and its range of application is more and more wider.This bright purpose provides a kind of nylon black and active dye.

Summary of the invention

Technical problem to be solved by this invention is develop a kind of environment-friendly type, and application performance to be excellent, nylon black and active dye that suitability is strong and preparation method thereof.

In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of black and active dye, and the structural formula of these reactive dyestuffs is shown in formula I:

The present invention also provides the preparation method of above-mentioned reactive dyestuffs, comprises the steps:

1), 1#base preparation:

In dissolving vessel, add beta naphthal, water of a small amount of end, NaOH solution, sodium-chlor, yellow soda ash, the complete molten beta naphthal solution that gets; Then beta naphthal solution is poured fast into coupling in the 6-nitro-1,2,4-sulfonic acid solution; Get 1#base, a standby step complexing;

2), chromaking agent preparation

In reactor, add chromium trioxide, formic acid is slowly dripped in the chromium trioxide, react to get the chromaking agent, a standby step complexing;

3), 1:1 complexes preparation

With step 1) gained 1#base and step 2) agent of gained chromaking reacts to get the 1:1 complex compound, standby two step complexings;

4), 2#base preparation

The J acid solution is added in the 6-nitro-1,2,4-sulfonic acid solution fast, react to get 2#base, standby two step complexings;

5), the preparation of 1:2 complex compound

With step 3) gained 1:1 complex compound pours among the 2#base, reacts to get the 1:2 complex compound, standby two step condensations;

6), a step condensation

Para-ester solution is added drop-wise in the cyanuric chloride, reacts to get a contracting thing, standby two step condensations;

7), two step condensations

With step 6) a contracting thing adds step 5) in the gained 1:2 complex compound, react to get two contracting things, the standby hydrolysis;

8), hydrolysis

With step 7) gained two contracting things transfer to 9-9.5 with yellow soda ash with pH, are warming up to 47-52 ℃ of reaction, and reaction is finished, and with hydrochloric acid pH is pulled back to 5.5-6.0, is cooled to 15-25 ℃, gets the formula I dye solution.

Particularly, the preparation method of formula I reactive dyestuffs comprises the steps:

1), 1#base preparation:

In reactor, add the 6-nitro-1,2,4-sulfonic acid, add water of a small amount of end and trash ice, the NaOH solution with 30% is adjusted to 2.0-2.5 with pH, complete molten standby coupling, get 6-nitro-1,2,4-sulfonic acid solution, in dissolving vessel, add beta naphthal, water of a small amount of end, 30% NaOH solution, sodium-chlor, yellow soda ash is warming up to 80 ℃ and is stirred to entirely moltenly, gets beta naphthal solution; Then beta naphthal solution is poured fast into coupling in the 6-nitro-1,2,4-sulfonic acid solution; PH is between 10-10.5 after the coupling, and temperature is kept 40-45 ℃, and insulation reaction gets 1#base, a standby step complexing;

2), chromaking agent preparation

In reactor, add chromium trioxide and Di Shui, be warming up to 40 ℃, formic acid is dripped in chromium trioxide, dropwise, be warming up to 75-80 ℃, be incubated 3-4 hour; Reaction is finished, and gets the chromaking agent, a standby step complexing;

3), 1:1 complexes preparation

With step 1) gained 1#base and step 2) agent of gained chromaking pours in the reactor, and pH is transferred to 4-4.5, is warming up to 100-120 ℃, be incubated 3-4 hour, pH is continued to be adjusted downward between the 1.8-2.2, continue insulation 6-10 hour, get the 1:1 complex compound, standby two step complexings;

4), 2#base preparation

In reactor, add the 6-nitro-1,2,4-sulfonic acid, add end water and trash ice, with NaOH solution pH is adjusted to 2.0-7.5, entirely molten, get 6-nitro-1,2,4-sulfonic acid solution, standby coupling; Add J acid in the reactor, with sodium hydroxide solution pH is transferred to 6.0-9.5, gets the J acid solution, the J acid solution is joined step 4 fast) 6-nitro-1,2, in the 4-acid oxysome solution, the complete pH of coupling is at 6.5-9.5, temperature 25-60 ℃, be incubated 6-20 hour, reaction is finished, and gets 2#base, standby two step complexings;

5), the preparation of 1:2 complex compound

With step 4) gained 2#base is warming up to 75-80 ℃, with step 3) gained 1:1 complex compound pours among the 2#base, adjust pH at 7.5-8.0 with NaOH solution, holding temperature is at 75-80 ℃, and reaction is finished, and 2#base disappears, be cooled to 30-40 ℃, pH pulls back to 5.0-6.0, gets the 1:2 complex compound, standby two step condensations;

6), a step condensation

In dissolving vessel, add para-ester and water, transfer pH at 4-4.5 with yellow soda ash, be stirred to entirely moltenly, get para-ester solution, in reactor, add end water and trash ice, add cyanuric chloride, ice mill 5-10 minute is added drop-wise to para-ester solution in the cyanuric chloride again, regulate pH at 2-2.5 with sodium carbonate solution, reaction is finished, and gets a contracting thing, standby two step condensations;

7), two step condensations

With step 6) a contracting thing adds step 5) in the gained 1:2 complex compound, keep pH at 5.5-6.0 with yellow soda ash, temperature was 40-45 ℃ of insulation 2-3 hour, and reaction is finished, and gets two contracting things, the standby hydrolysis;

8), hydrolysis

With step 7) gained two contracting things transfer to 9-9.5 with yellow soda ash with pH, are warming up to 47-52 ℃ of reaction, are incubated 3-4 hour, reaction is finished, and with hydrochloric acid pH is pulled back to 5.5-6.0, is cooled to 15-25 ℃, get the formula I dye solution, filter, filter cake making beating spraying gets product.

The present invention also provides the application of a kind of above-mentioned formula I reactive dyestuffs in dyeing nylon.

Wherein, the structure of 6-nitro-1,2,4-sulfonic acid is as follows:

The structural formula of para-ester is as follows:

Cyanuric chloride, structural formula is

Be reduced among the present invention

J acid structural formula is:

。

The beneficial effect that the present invention has:

The reactive dyestuffs that the present invention makes are environment-friendly type, and application performance is excellent, and suitability is strong, is particularly useful for dyeing nylon.

Embodiment

The invention will be further described below in conjunction with specific embodiment, but do not limit protection scope of the present invention.

Embodiment 1:

A kind of black and active dye, the structural formula of these reactive dyestuffs is shown in formula I:

The preparation method of formula I reactive dyestuffs comprises the steps:

1), 1#base preparation:

Add 6-nitro-1,2,4-sulfonic acid 29.5g in reactor, add water of a small amount of end and trash ice, with the NaOH solution of 30wt% pH is adjusted to 2.0-2.5, complete molten 6-nitro-1,2,4-sulfonic acid solution is for coupling; In dissolving vessel, add beta naphthal 15.1g, water of a small amount of end, the NaOH solution of 15g 30wt%, 5.0g sodium-chlor, 10g yellow soda ash is warming up to 80 ℃ and is stirred to entirely moltenly, gets beta naphthal solution; Then beta naphthal solution is poured fast into coupling in the 6-nitro-1,2,4-sulfonic acid solution, pH is between 10-10.5 after the coupling, and temperature is kept 40-45 ℃, is incubated four hours, gets 1#base, a standby step complexing;

2), chromaking agent preparation

Water at the bottom of adding chromium trioxide 10g and the 50mL is warming up to about 40 ℃ in reactor, and formic acid 30g is slowly dripped in the chromium trioxide, dropwises, and is warming up to 75-80 ℃, is incubated 3 hours, and reaction is finished, and gets the chromaking agent, for a step complexing;

3), 1:1 complexes preparation

With step 1) gained 1#base and step 2) agent of gained chromaking pours in the reactor, and pH is transferred between the 4-4.5, is warming up to 100-120 ℃, be incubated 4 hours, pH is continued to be adjusted downward between the 1.8-2.2, continue insulation 8 hours, get the 1:1 complex compound, standby two step complexings;

4), 2#base preparation

In reactor, add 6-nitro-1,2,4-sulfonic acid 29.5g, add water of a small amount of end and trash ice, with the NaOH solution of 30wt% pH is adjusted to 2.0-2.5, entirely molten, get 6-nitro-1,2,4-sulfonic acid solution, for coupling; Add 23.4gJ acid in the reactor, sodium hydroxide solution with 30wt% transfers to pH between the 6.0-7.5, gets the J acid solution, and J acid is joined step 4 fast) 6-nitro-1,2, in the 4-acid oxysome solution, the complete pH of coupling between 6.5-7.5, temperature 25-35 ℃, be incubated 7 hours, reaction is finished, 2#base, standby two step complexings;

5), the preparation of 1:2 complex compound

With step 4) gained 2#base magma is warming up to 75-80 ℃, with step 3) gained 1:1 complex compound pours among the 2#base, adjust pH between 7.5-8.0 with the NaOH solution of 30wt%, holding temperature is between 75-80 ℃, and reaction is finished, and 2#base disappears, be cooled to 30-40 ℃, pH pulls back to 5.0-6.0, gets the 1:2 complex compound, standby two step condensations;

6), a step condensation

In dissolving vessel, add para-ester 29g and a small amount of water, transfer to pH at 4-4.5 with yellow soda ash, be stirred to entirely molten, get para-ester solution, in reactor, add water of a small amount of end and trash ice, add again cyanuric chloride 18.5g, ice mill 8 minutes, para-ester solution is added drop-wise in the cyanuric chloride, with 5.3g yellow soda ash chemical solution, regulates pH between 2-2.5, be incubated 3 hours, reaction is finished, and gets a contracting thing, standby two step condensations;

7), two step condensations

With step 6) a contracting thing adds step 5) in the gained 1:2 complex compound, keep pH at 5.5-6.0 with yellow soda ash, temperature be incubated 3 hours at 40-45 ℃, and reaction is finished, and gets two contracting things, for being hydrolyzed;

8), hydrolysis

With step 7) gained two contracting things transfer to 9-9.5 with yellow soda ash with pH, are warming up to 47-52 ℃, are incubated 3 hours, reaction is finished, and with hydrochloric acid pH is pulled back to 5.5-6.0, is cooled to 15-25 ℃, get formula I reactive dyestuffs solution, filter, filter cake making beating spraying gets product.

Embodiment 2

A kind of preparation method of formula I black and active dye comprises the steps:

1), 1#base preparation:

Add 6-nitro-1,2,4-sulfonic acid 29.5g in reactor, add water of a small amount of end and trash ice, with the NaOH solution of 30wt% pH is adjusted to 2.0-2.5, complete molten 6-nitro-1,2,4-sulfonic acid solution is for coupling; In dissolving vessel, add beta naphthal 15.1g, water of a small amount of end, the NaOH solution of 15g 30wt%, 5.0g sodium-chlor, 10g yellow soda ash is warming up to 80 ℃ and is stirred to entirely moltenly, gets beta naphthal solution; Then beta naphthal solution is poured fast into coupling in the 6-nitro-1,2,4-sulfonic acid solution, pH is between 10-10.5 after the coupling, and temperature is kept 40-45 ℃, is incubated four hours, gets 1#base, a standby step complexing;

2), chromaking agent preparation

Water at the bottom of adding chromium trioxide 10g and the 50mL is warming up to about 40 ℃ in reactor, and formic acid 30g is slowly dripped in the chromium trioxide, dropwises, and is warming up to 75-80 ℃, is incubated 4 hours, and reaction is finished, and gets the chromaking agent, for a step complexing;

3), 1:1 complexes preparation

With step 1) gained 1#base and step 2) agent of gained chromaking pours in the reactor, and pH is transferred between the 4-4.5, is warming up to 100-120 ℃, be incubated 3 hours, pH is continued to be adjusted downward between the 1.8-2.2, continue insulation 7 hours, get the 1:1 complex compound, standby two step complexings;

4), 2#base preparation

Add 6-nitro-1,2,4-sulfonic acid 29.5g in the reactor, add water of a small amount of end and trash ice, with the NaOH of 30wt% pH is adjusted to 6.0-7.5, entirely molten, get 6-nitro-1,2,4-sulfonic acid solution, for coupling; In reactor, add 23.4gJ acid, sodium hydroxide with 30wt% transfers to pH between the 7.5-8.5, gets the J acid solution, and the J acid solution is joined step 4 fast) 6-nitro-1,2, in the 4-acid oxysome solution, the complete pH of coupling between 8.5-9.5, temperature 45-60 ℃, be incubated 15 hours, reaction is finished, and gets 2#base, standby two step complexings;

5), the preparation of 1:2 complex compound

With step 4) gained 2#base magma is warming up to 75-80 ℃, with step 3) gained 1:1 complex compound pours among the 2#base, adjust pH between 7.5-8.0 with the NaOH solution of 30wt%, holding temperature is between 75-80 ℃, and reaction is finished, and 2#base disappears, be cooled to 30-40 ℃, pH pulls back to 5.0-6.0, gets the 1:2 complex compound, standby two step condensations;

6), a step condensation

In dissolving vessel, add para-ester 29g and a small amount of water, transfer to pH at 4-4.5 with yellow soda ash, be stirred to entirely molten, get para-ester solution, in reactor, add water of a small amount of end and trash ice, add again cyanuric chloride 18.5g, ice mill 8 minutes, para-ester solution is added drop-wise in the cyanuric chloride, with 5.3g yellow soda ash chemical solution, regulates pH between 2-2.5, be incubated 3 hours, reaction is finished, and gets a contracting thing, standby two step condensations;

7), two step condensations

With step 6) a contracting thing adds step 5) in the gained 1:2 complex compound, keep pH at 5.5-6.0 with yellow soda ash, temperature be incubated 3 hours at 40-45 ℃, and reaction is finished, and gets two contracting things, for being hydrolyzed;

8), hydrolysis

With step 7) gained two contracting things transfer to 9-9.5 with yellow soda ash with pH, are warming up to 47-52 ℃, are incubated 4 hours, reaction is finished, and with hydrochloric acid pH is pulled back to 5.5-6.0, is cooled to 15-25 ℃, get formula I reactive dyestuffs solution, filter, filter cake making beating spraying gets product.

The application performance table of black and active dye of the present invention

Metal to-metal contact: 4-5 level

Wet friction: 4 grades

Degree of fixation: 95%

Solubleness: 125g/L

Dyestuff of the present invention and preparation of dyestuff method are described by specific embodiment.Those skilled in the art can use for reference content appropriate change raw material of the present invention, the links such as processing condition realize the present invention, its relevant change does not all break away from content of the present invention, so similarly replace and change will become apparent to those skilled in the art that and all is deemed to be included within the scope of the present invention.

Claims (3)

1. black and active dye, it is characterized in that: the structural formula of these reactive dyestuffs is shown in formula I:

2. the preparation method of the described reactive dyestuffs of claim 1, it is characterized in that: the method comprises the steps:

1), 1#base preparation:

In dissolving vessel, add beta naphthal, water of a small amount of end, NaOH solution, sodium-chlor, yellow soda ash, the complete molten beta naphthal solution that gets; Then beta naphthal solution is poured fast into coupling in the 6-nitro-1,2,4-sulfonic acid solution; Get 1#base, a standby step complexing;

2), chromaking agent preparation

In reactor, add chromium trioxide, formic acid is slowly dripped in the chromium trioxide, react to get the chromaking agent, a standby step complexing;

3), 1:1 complexes preparation

With step 1) gained 1#base and step 2) agent of gained chromaking reacts to get the 1:1 complex compound, standby two step complexings;

4), 2#base preparation

The J acid solution is added in the 6-nitro-1,2,4-sulfonic acid solution fast, react to get 2#base, standby two step complexings;

5), the preparation of 1:2 complex compound

With step 3) gained 1:1 complex compound pours among the 2#base, reacts to get the 1:2 complex compound, standby two step condensations;

6), a step condensation

Para-ester solution is added drop-wise in the cyanuric chloride, reacts to get a contracting thing, standby two step condensations;

7), two step condensations

With step 6) a contracting thing adds step 5) in the gained 1:2 complex compound, react to get two contracting things, the standby hydrolysis;

8), hydrolysis

With step 7) gained two contracting things transfer to 9-9.5 with yellow soda ash with pH, are warming up to 47-52 ℃ of reaction, and reaction is finished, and with hydrochloric acid pH is pulled back to 5.5-6.0, is cooled to 15-25 ℃, gets the formula I dye solution.

3. method according to claim 2, it is characterized in that: the method comprises the steps:

1), 1#base preparation:

In reactor, add the 6-nitro-1,2,4-sulfonic acid, add water of a small amount of end and trash ice, the NaOH solution with 30% is adjusted to 2.0-2.5 with pH, complete molten standby coupling, get 6-nitro-1,2,4-sulfonic acid solution, in dissolving vessel, add beta naphthal, water of a small amount of end, 30% NaOH solution, sodium-chlor, yellow soda ash is warming up to 80 ℃ and is stirred to entirely moltenly, gets beta naphthal solution; Then beta naphthal solution is poured fast into coupling in the 6-nitro-1,2,4-sulfonic acid solution; PH is between 10-10.5 after the coupling, and temperature is kept 40-45 ℃, and insulation reaction gets 1#base, a standby step complexing.

2), chromaking agent preparation

In reactor, add chromium trioxide and Di Shui, be warming up to 40 ℃, formic acid is dripped in chromium trioxide, dropwise, be warming up to 75-80 ℃, be incubated 3-4 hour; Reaction is finished, and gets the chromaking agent, a standby step complexing.

3), 1:1 complexes preparation

With step 1) gained 1#base and step 2) agent of gained chromaking pours in the reactor, and pH is transferred to 4-4.5, is warming up to 100-120 ℃, be incubated 3-4 hour, pH is continued to be adjusted downward between the 1.8-2.2, continue insulation 6-10 hour, get the 1:1 complex compound, standby two step complexings.

4), 2#base preparation

In reactor, add the 6-nitro-1,2,4-sulfonic acid, add end water and trash ice, with NaOH solution pH is adjusted to 2.0-7.5, entirely molten, get 6-nitro-1,2,4-sulfonic acid solution, standby coupling; Add J acid in the reactor, with sodium hydroxide solution pH is transferred to 6.0-9.5, gets the J acid solution, the J acid solution is joined step 4 fast) 6-nitro-1,2, in the 4-acid oxysome solution, the complete pH of coupling is at 6.5-9.5, temperature 25-60 ℃, be incubated 6-20 hour, reaction is finished, and gets 2#base, standby two step complexings.

5), the preparation of 1:2 complex compound

With step 4) gained 2#base is warming up to 75-80 ℃, with step 3) gained 1:1 complex compound pours among the 2#base, adjust pH at 7.5-8.0 with NaOH solution, holding temperature is at 75-80 ℃, and reaction is finished, and 2#base disappears, be cooled to 30-40 ℃, pH pulls back to 5.0-6.0, gets the 1:2 complex compound, standby two step condensations;

6), a step condensation

In dissolving vessel, add para-ester and water, transfer pH at 4-4.5 with yellow soda ash, be stirred to entirely moltenly, get para-ester solution, in reactor, add end water and trash ice, add cyanuric chloride, ice mill 5-10 minute is added drop-wise to para-ester solution in the cyanuric chloride again, regulate pH at 2-2.5 with sodium carbonate solution, reaction is finished, and gets a contracting thing, standby two step condensations;

7), two step condensations

With step 6) a contracting thing adds step 5) in the gained 1:2 complex compound, keep pH at 5.5-6.0 with yellow soda ash, temperature was 40-45 ℃ of insulation 2-3 hour, and reaction is finished, and gets two contracting things, the standby hydrolysis;

8), hydrolysis

With step 7) gained two contracting things transfer to 9-9.5 with yellow soda ash with pH, are warming up to 47-52 ℃ of reaction, are incubated 3-4 hour, reaction is finished, and with hydrochloric acid pH is pulled back to 5.5-6.0, is cooled to 15-25 ℃, get the formula I dye solution, filter, filter cake making beating spraying gets product.