阅读说明：本技术 一种以萘四甲酸为原料的棕色还原染料、制备方法及应用 (Brown vat dye using naphthalene tetracarboxylic acid as raw material, preparation method and application ) 是由 孙东洲 魏继武 金肇岩 于 2019-11-26 设计创作，主要内容包括：本发明属于萘四甲酸还原染料制备技术领域,具体涉及一种以萘四甲酸为原料的棕色还原染料、制备方法及应用。该棕色还原染料包括两种化合物。该棕色还原染料是一种新结构的棕色还原染料,为商品化染料提供了一种新配色方案,丰富了棕色系原染料及商品化棕色染料的可选范围；而且,本发明提供的含有新结构的棕色还原染料的商品化染料是将还原棕染料与其结构近似的还原红14、还原红15/还原橙7相混合,制得的染料色差小、上染率可高达98％,色牢度好,耐光晒牢度可达到6级。(The invention belongs to the technical field of preparation of naphthalene tetracarboxylic acid vat dyes, and particularly relates to a brown vat dye taking naphthalene tetracarboxylic acid as a raw material, a preparation method and application thereof. The brown vat dye comprises two compounds. The brown vat dye is a brown vat dye with a new structure, provides a new color matching scheme for commercial dyes, and enriches the selectable range of brown series original dyes and commercial brown dyes; in addition, the commercial dye containing the brown vat dye with the new structure provided by the invention is prepared by mixing the vat brown dye with vat red 14 and vat red 15/vat orange 7 which have similar structures, and the prepared dye has small color difference, high dye uptake rate of 98 percent, good color fastness and light fastness of 6 grades.)

1. A brown vat dye using naphthalene tetracarboxylic acid as a raw material is characterized by comprising two compounds shown as the following structures (I) and (II):

2. a method for preparing a brown vat dye according to claim 1, comprising the steps of:

the method comprises the following steps of carrying out condensation reaction on 4-methoxy-2-nitroaniline and 1,4,5, 8-naphthalene tetracarboxylic acid, wherein the solvent of the condensation reaction is water, the catalyst is glacial acetic acid, and the volume concentration of the glacial acetic acid in a reaction system is 9-15%.

3. The method for preparing brown vat dye according to claim 2, wherein the condensation reaction is carried out at a temperature of 130 ℃ and 138 ℃ and a pressure of 0.1-0.6 MPa.

4. The method for preparing brown vat dye according to claim 2, wherein the mass ratio of 4-methoxy-2-nitroaniline to 1,4,5, 8-naphthalenetetracarboxylic acid is 9-11: 10-12.

5. Use of a brown vat dye starting from naphthalenetetracarboxylic acid in commercial dyes, characterized in that the commercial dyes comprise i) a brown vat dye starting from naphthalenetetracarboxylic acid according to claim 1; ii) reduced red 14; and iii) vat red 15 or vat orange 7.

6. The use according to claim 5, wherein the commercial dye comprises 70-80 wt% of a dispersant.

7. The use according to claim 6, wherein the dispersant is one or more of sodium lignosulfonate, dispersant MF, dispersant NNO, dispersant CNF.

8. The use according to claim 6, wherein the mass ratio of the brown vat dye to the vat red 14 in the commercial dye is 1-3: 4-8; the mass ratio of the brown vat dye to vat red 15/vat orange 7 is 1: 0.3-0.6.

9. A method for preparing a commercial dye, which is characterized by comprising the following steps:

adding the filter cake of vat red 14, vat brown filter cake and the filter cake of vat red 15/vat orange 7 into water, adding a dispersing agent for pulping, and carrying out flash evaporation or spray drying after sand grinding and dispersion to obtain the red brown or yellow brown dye.

10. The method of claim 9, wherein the amount of water is 2 to 4 times the total weight of all the dye cake and the dispersing agent.

Technical Field

The invention belongs to the technical field of preparation of naphthalene tetracarboxylic acid vat dyes, and particularly relates to a brown vat dye taking naphthalene tetracarboxylic acid as a raw material, a preparation method and application thereof.

Background

The vat dye is a dye which is reduced under an alkaline condition to color a fiber, and then oxidized to restore the original insoluble dye on the fiber to dye the fiber.

The classic vat orange 7 (CAS: 4426-06-0) and vat red 15 (CAS: 4216-02-8) belong to high-grade vat dyes which are successfully researched and developed and are relatively early commercialized, and are mostly used for dyeing and printing cotton fibers, the vat orange 7 is orange red powder in appearance, is insoluble in water and common organic solvents, is orange yellow when dissolved in concentrated sulfuric acid, and is blue solution after being reduced by alkaline sodium hydrosulfite solution, has good affinity to the cotton fibers, is bright orange in color and has good covering power, the vat red 15 is dark red powder in appearance, is insoluble in water and common organic solvents, is dark red solution when dissolved in concentrated sulfuric acid, and is blue solution after being reduced by the alkaline sodium hydrosulfite solution, is mauve on the cotton fibers and has good covering power Soaping resistance, ironing resistance and rubbing fastness, especially, the vat orange 7 has extremely bright orange which is difficult to compare with other orange dyes. The vat red 15 and the vat orange 7 are mostly obtained by condensing 1,4,5, 8-naphthalene tetracarboxylic acid and o-phenylenediamine in acetic acid to obtain an intermediate product, then separating according to different solubilities of different components in the intermediate product in a mixed solution of ethanol, water and potassium hydroxide, and finally adding acid in water respectively to separate out.

For red orange system, vat red 15, vat orange 7 or a mixture of both vat red 14 is mostly used (vat dye vat red 14([ CAS: 8005-56-9]) is prepared by mixing trans-form orange 7 and cis-form vat red 15 which are isomers with each other in proportion) and blending.

For brown-containing systems, the brown-containing systems are mostly prepared by mixing and dispersing a single brown dye and a dispersing agent in the prior art. For example, chinese patent application CN201010263913.4 discloses an environment-friendly brown vat dye and a commercial manufacturing method thereof, wherein the environment-friendly brown vat dye is prepared by pulping 30% by weight of c.i. vat brown 1, 1-5% by weight of dispersant 610, 1-5% by weight of dispersant 615, 25-35% by weight of dispersant MF, 3-7% by weight of dispersant 83A, 15-25% by weight of dispersant DN14 and 6-10% by weight of dispersant 85A, grinding, drying, and spraying 0-2% by weight of dust control oil. However, the dye has the problems of large color difference, incapability of meeting the requirements of customers and the like.

Disclosure of Invention

In order to solve the above problems in the prior art, an object of the present invention is to provide a brown vat dye using naphthalenetetracarboxylic acid as a raw material, which can be used to prepare a commercial brown dye having the advantages of low color difference, high fastness, good abrasion resistance, etc.

Another object of the present invention is to provide a method for preparing the brown vat dye.

It is a further object of the present invention to provide the use of the brown vat dye in commercial dyes.

It is still another object of the present invention to provide a method for preparing the commercial dye.

In order to achieve the above object, one of the technical solutions of the present invention is as follows:

a brown vat dye using naphthalene tetracarboxylic acid as a raw material comprises compounds shown as the following formulas (I) and (II):

the invention also provides a preparation method of the brown vat dye, which comprises the following steps:

the method comprises the following steps of carrying out condensation reaction on 4-methoxy-2-nitroaniline and 1,4,5, 8-naphthalene tetracarboxylic acid, wherein the solvent of the condensation reaction is water, the catalyst is glacial acetic acid, and the volume concentration of the glacial acetic acid in a reaction system is 9-15%.

Preferably, the reaction temperature of the condensation reaction is 130-138 ℃, and the reaction pressure is 0.1-0.6 MPa.

Preferably, the condensation reaction is carried out for 5 to 9 hours; more preferably 6 to 8 hours.

Preferably, the mass ratio of the 1,4,5, 8-naphthalene tetracarboxylic acid to the 4-methoxy-1, 2-o-phenylenediamine is 9-11: 10-12.

As a preferred embodiment, the method for preparing the brown vat dye comprises the following steps:

adding water into a reaction container, adding acetic acid serving as a catalyst under stirring, wherein the volume concentration of the acetic acid in the system is 9-15%, adding 1,4,5, 8-naphthalene tetracarboxylic acid and 4-methoxy-1, 2-o-phenylenediamine, sealing the reactor, heating to 130-138 ℃, keeping the temperature and pressure, stirring for reaction for 5-9 hours, cooling to 80-90 ℃, filtering while hot, washing a filter cake to be neutral by using hot water at 60-90 ℃, drying and crushing the filter cake into reddish brown powder; wherein the mass ratio of the 1,4,5, 8-naphthalene tetracarboxylic acid to the 4-methoxy-1, 2-o-phenylenediamine is 9-11: 10-12.

Preferably, in this embodiment, the 1,4,5, 8-naphthalenetetracarboxylic acid has a purity of > 96%; the purity of the 4-methoxy-1, 2-o-phenylenediamine is more than 98 percent.

Another embodiment of the present invention provides the use of the brown vat dye in commercial dyes comprising i) the brown vat dye of claim 1 starting from naphthalenetetracarboxylic acid; ii) reduced red 14; and iii) vat red 15 or vat orange 7.

Preferably, the commercial dye further comprises 70-80 wt% of a dispersant.

Further preferably, the dispersant is one or more of sodium lignosulfonate, dispersant MF, dispersant NNO and dispersant CNF.

The dispersing agent is of a structure conventional in the field and can be purchased in the market.

Preferably, the mass ratio of the brown vat dye to the vat red 14 in the commercial dye is 1-3: 4-8.

Further preferably, the mass ratio of the brown vat dye to the vat red 14 is 2-3: 5-6.

In a preferred embodiment, the mass ratio of the brown vat dye to the vat red 14 is 3: 5.

Preferably, the mass ratio of the brown vat dye to vat red 15 or vat orange 7 is 1: 0.3-0.6.

Further preferably, the mass ratio of the brown vat dye to vat red 15 or vat orange 7 is 1: 0.33-0.53.

The invention also provides a preparation method of the commercial dye, which comprises the following steps:

adding the filter cake of vat red 14, vat brown filter cake and the filter cake of vat red 15/vat orange 7 into water, adding a dispersing agent for pulping, and carrying out flash evaporation or spray drying after sand grinding and dispersion to obtain the red brown or yellow brown dye.

Preferably, the amount of water is 2 to 4 times the total weight of all the dye press cake and dispersant.

Preferably, the water content of each filter cake during the preparation of the commercial dye does not exceed 3%. To facilitate calculation of the true dye content of each filter cake, the weight of dye on dry basis in the filter cake should be calculated.

Compared with the prior art, the brown vat dye, the commercial dye containing the brown vat dye and the preparation method thereof provided by the invention have the following beneficial effects:

(1) the invention provides a brown vat dye with a new structure and a brown commercial dye with a new color matching scheme, which enriches the selectable range of brown series original dyes and commercial brown dyes;

(2) the commercial dye containing brown vat dye with new structure provided by the invention is prepared by mixing vat brown dye with vat red 14 and vat red 15/vat orange 7 with similar structures, and the prepared dye has small color difference, high dye uptake rate up to 98%, good color fastness and light fastness up to 6 levels.

(3) The preparation method of the brown vat dye provided by the invention takes ethanol as a catalyst and water as a main solvent medium, so that the dosage of ethanol is reduced, and on one hand, the dosage of an organic solvent is reduced, and the discharge amount of three wastes is reduced; on the other hand, the color light and the color strength of the brown vat dye are improved; tests show that the commercial dye prepared from the brown vat dye prepared from the catalytic amount of ethanol has moderate color light and color strength, and is suitable for color matching; and the dye has better dye uptake and light fastness.

Detailed Description

In order to make the purpose and technical solution of the embodiments of the present invention clearer, the technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Unless otherwise specified, "parts" as used in the following examples refer to parts by volume if the corresponding substance is a liquid; parts by weight are meant if the corresponding substance is a solid. The dispersant used in the present invention is available from the company dicyclic adjuvant, Anyang, unless otherwise specified.