CN103044962B - Aniline black pigment producing method - Google Patents

Abstract

The invention discloses an aniline black pigment producing method. The aniline black pigment producing method comprises the following steps of: taking aniline as a raw material, and adding hydrochloric acid to synthesize an aniline hydrochloride solution; adding a hydroxyl copper phosphate catalyst, and dripping hydrogen peroxide; and after reaction, filtering, cleaning, drying and grinding to obtain aniline black pigment. In the aniline black pigment producing method, dichromate is not taken as an oxidant, thus avoiding chromium pollution; the hydroxyl copper phosphate catalyst coordinates with the hydrogen peroxide oxidant, thus improving the yield of the aniline black pigment; the produced obtained aniline black pigment is pure in color and luster and is blue phase black; and the production is simple and convenient.

Description

A kind of production method of nigrosine pigment

Technical field

That the present invention relates to is the preparation method of a kind of nigrosine pigment (Aniline Black)

Background technology

Nigrosine (Aniline Black), Colour index number is Pigment Black 1, it is middle black, spectral absorption is wide and dispersion is little, there is very superior covering power, even if very tiny particle, also almost produces without coacervation in use, this makes it be very easy to disperse in various media.The essential distinction of nigrosine and carbon black is that it does not have electroconductibility, and tinting strength is poorer than carbon black.Be applied at present coating, paint and printing-ink, particularly need occasion and the inefficient occasion of carbon black of color and luster effect as black velvet.In addition, nigrosine pigment, also for the carbon dust of laser printer, is made positive charge conditioning agent.

Between 1860-1863, on fiber, the technology of synthetic nigrosine is just succeeded in developing.The method of the synthetic nigrosine pigment of people is more or less the same therewith now, is dissolved in the vitriol oil by aniline, under the existence of oxidative catalyst, uses sodium dichromate 99 to be oxidized and to generate nigrosine as oxygenant.

In this technique, owing to having used sodium dichromate 99 as oxygenant, not only form in process of production reluctant a large amount of chromate waste water, also make in nigrosine pigment chromium content high, it is restricted in a lot of application, particularly the application in textile printing and dyeing, is very restricted.

In Japanese Laid-Open Patent Publication (JP 2000-72974), use this Green Oxidant of hydrogen peroxide to produce nigrosine pigment, avoided pollution of chromium.In this patent, used the salt of iron (II), iron (III) as catalyzer, but the nigrosine yield that the method is produced is low, pigment coloured light inclined to one side ruddiness.

Summary of the invention

The object of this invention is to provide a kind of novel method of preparing nigrosine pigment, use hydrogen peroxide as oxygenant to overcome, be used in conjunction with the salt of iron (II), iron (III) as Catalyst Production nigrosine pigment, exist that yield is low, the problem of the inclined to one side ruddiness of pigment coloured light.

Nigrosine pigment involved in the present invention has following structure:

Nigrosine method for preparing pigment of the present invention:

(1) synthetic: use aniline as raw material, add hydrochloric acid to synthesize anilinechloride solution, add hydroxyl cupric phosphate catalyzer, drip hydrogen peroxide, after question response completes, filter, filter cake washes with water to filtrate colourless.

(2) dry: filter cake is dry in baking oven;

(3) pulverize: dried pigment is put into grinding machine, wear into fine powder, obtain finished product nigrosine pigment.

The cupric phosphate catalyzer that Ben Mingfa uses is following structure:

Cu ₂(OH) _x(PO ₄) _y

Wherein x=0-1, y=0-1, is green crystals, works as x=1, when y=1, its structural formula is: Cu ₂(OH) PO ₄, be also referred to as hydroxyl cupric phosphate.

Compared with the technology that the present invention produces nigrosine pigment with existing sodium dichromate 99 method for oxidation, this technology is not used dichromate as oxygenant, does not contain chromium element in product, has avoided pollution of chromium.

The present invention has used hydroxyl cupric phosphate as catalyzer, makes hydrogen peroxide oxidation, has improved the yield of nigrosine pigment, and makes pigment coloured light approach the product that uses sodium dichromate 99 technique, produces simple and convenient.

The present invention uses hydroxyl cupric phosphate to coordinate with hydrogen peroxide oxidant for catalyzer, can effectively anilinechloride be oxidized into nigrosine pigment, hydroxyl cupric phosphate catalyzer has the advantages such as selectivity is high, catalytic activity is high, reaction conditions is gentle, for the preparation of nigrosine pigment, can improve transformation efficiency, the product coloured light obtaining is pure, is blue phase-black, substantially reaches the level of sodium dichromate 99 oxidizing process product.

The molecular formula of hydroxyl cupric phosphate is Cu ₂(OH) PO ₄, can be by Chinese patent " catalyst for clean catalytic oxidation of aromatic hydrocarbons and preparation method thereof " (application number: disclosed method preparation 98106587).

Embodiment

Nigrosine method for preparing pigment of the present invention:

(1) synthetic: to use aniline as raw material, add hydrochloric acid to synthesize the anilinechloride solution that aniline weight percent is 6-15%, add the hydroxyl cupric phosphate catalyzer with respect to aniline weight 0.5-3%, at 35-60 DEG C, drip weight percent and be 30% aqueous hydrogen peroxide solution, its add-on is the 350-450% of aniline weight, after adding in 15-60 minute, at 30-75 DEG C of insulation 1-2 hour, filter, filter cake washes with water to filtrate colourless.

(2) dry: filter cake is dried at 120 DEG C-170 DEG C;

(3) pulverize: dried pigment is put into grinding machine, be milled to mean particle size and be less than 10 microns, obtain finished product nigrosine pigment.

Because the catalyzer using is water-fast green crystal, and in product, be difficult to separate, so hydroxyl cupric phosphate catalyzer add-on is not beneficial to 3% of aniline weight, many can affect product coloured light.

Embodiment 1:

In 500ml there-necked flask, add 200ml water, adding 12 gram weight per-cents is 30% hydrochloric acid, stir the lower 9.9 grams of aniline that drip, complete molten after, add 0.28 gram (for aniline weight 2.8%) hydroxyl cupric phosphate catalyzer, be warming up to 45 DEG C, dripping 40 gram weight per-cents is 30% superoxol, completes dropping at 35-40 minute, at 50 DEG C, be incubated 1 hour, filter, filter cake, is dried 2 hours to colourless with about 500ml water washing at 140 DEG C, obtain 9.5 grams of nigrosines, in aniline, yield is 96%, and coloured light is that blue light is black.

Embodiment 2:

In 500ml there-necked flask, add 200ml water, adding 12 gram weight per-cents is 30% hydrochloric acid, stir the lower 9.9 grams of aniline that drip, complete molten after, add 0.05 gram (for aniline weight 0.5%) hydroxyl cupric phosphate catalyzer, be warming up to 50 DEG C, dripping 35 gram weight per-cents is 30% superoxol, in 45-50 minute, completes dropping, at 55 DEG C, is incubated 2 hours, filter, filter cake, is dried 2 hours to colourless with about 500ml water washing at 140 DEG C, obtains 9.0 grams of nigrosines, yield is 91%, and coloured light is that blue light is black.

Embodiment 3:

In 500ml there-necked flask, add 200ml water, adding 12 gram weight per-cents is 30% hydrochloric acid, stir the lower 9.9 grams of aniline that drip, complete molten after, add 0.1 gram (for aniline weight 1%) hydroxyl cupric phosphate catalyzer, be warming up to 35 DEG C, dripping 35 gram weight per-cents is 30% superoxol, in about 15-20 minute, adds dropping, at 35 DEG C, is incubated 1.5 hours, filter, filter cake, is dried 2 hours to colourless with 500ml water washing at 140 DEG C, obtains 9.3 grams of nigrosines, yield is 94%, and coloured light is that blue light is black.

Comparative example 1:

In 500ml there-necked flask, add 200ml water, add 12 gram of 30% hydrochloric acid, stir the lower 9.9 grams of aniline that drip, complete molten after, add 0.5 gram of ferrous sulfate as catalyzer, be warming up to 50 DEG C, dripping 35 gram weight per-cents is 30% superoxol, within approximately 20 minutes, add, at 55 DEG C, be incubated 1 hour, filter, filter cake is extremely colourless with 500ml water washing, at 140 DEG C, dry 2 hours, obtain 5.4 grams of green black powders, yield is 54.5%.

Claims (2)

1. a production method for nigrosine pigment, is characterized in that:

(1) synthetic: use aniline as raw material, add hydrochloric acid to synthesize anilinechloride solution, add hydroxyl cupric phosphate catalyzer, drip hydrogen peroxide, after question response completes, filter, filter cake washes with water to filtrate colourless;

(2) dry: filter cake is dry in baking oven;

(3) pulverize: dried pigment is put into grinding machine, wear into fine powder, obtain finished product nigrosine pigment.

2. a production method for nigrosine pigment, is characterized in that:

(1) synthetic: to use aniline as raw material, add hydrochloric acid to synthesize the anilinechloride solution that aniline weight percent is 6-15%, add the hydroxyl cupric phosphate catalyzer with respect to aniline weight 0.5-3%, at 35-60 DEG C, drip weight percent and be 30% aqueous hydrogen peroxide solution, aqueous hydrogen peroxide solution add-on is the 350-450% of aniline weight, after adding in 15-60 minute, at 30-75 DEG C of insulation 1-2 hour, filter, filter cake washes with water to filtrate colourless;

(2) dry: filter cake is dried at 120 DEG C-170 DEG C;

(3) pulverize: dried pigment is put into grinding machine, be milled to mean particle size and be less than 10 microns, obtain finished product nigrosine pigment.