CN112457684B

CN112457684B - Acid red dye for fur and preparation method and application thereof

Info

Publication number: CN112457684B
Application number: CN202011547422.2A
Authority: CN
Inventors: 王亮; 郑超斌; 郑红超
Original assignee: Beijing Fanbo Chemicals Co ltd
Current assignee: Beijing Fanbo Chemicals Co ltd
Priority date: 2020-12-24
Filing date: 2020-12-24
Publication date: 2022-12-06
Anticipated expiration: 2040-12-24
Also published as: CN112457684A

Abstract

The invention relates to an acid red dye for fur, a preparation method and application thereof, wherein the chemical structure of the acid red dye for fur is shown as a formula (I), and the preparation method comprises the following steps: the acid red dye for fur shown in the formula (I) is obtained by reacting a compound shown in the formula (II) and a compound shown in the formula (III) serving as raw materials under the catalysis of a catalyst. The invention develops a brand-new acid red dye, which has good compatibility and level-dyeing property with other dyes such as acid blue and acid yellow, has excellent fastness indexes such as perspiration fastness, light fastness, dry and wet rubbing fastness and washing fastness, and is very suitable for dyeing fur. The preparation method of the acid red dye for fur is simple and easy to operate, is very suitable for large-scale industrial production, and has good practicability. The acid red dye for fur prepared by the method has high yield and high purity.

Description

Acid red dye for fur and preparation method and application thereof

Technical Field

The invention belongs to the technical field of dyes, particularly relates to an acid red dye and a preparation method and application thereof, and particularly relates to an acid red dye for fur and a preparation method and application thereof.

Background

Along with the popularization of fur overcoats in common people, people pay more and more attention to the color light and fastness of furs, and particularly, the requirement on the light fastness and the dry and wet rubbing fastness of a red dye special for furs is high, so that the people in the fur field pay more attention to the fur.

Although the acid red 88 has good compatibility and level-dyeing property, the light fastness can hardly meet the requirements of customers; most of red dyes with good fastness disclosed in the prior art, such as an acid red dye composition disclosed in CN101177545A, mainly contains one or more components A with a structure shown in formula (I) and one or more components B with a structure shown in formula (II) or the acid red dye composition consists of one or more components A with a structure shown in formula (I) and one or more components B with a structure shown in formula (II), and red dyed fabrics with excellent performances of heat sensitivity, stability, bright color, sun resistance, washing resistance, sweat resistance and the like can be obtained by adjusting the proportion of different components; for example, CN1058277C, which is a novel non-carcinogenic monoazo acid red dye, does not contain carcinogenic mutagenic aromatic amine, and has dye fastness, such as solarization, soaping, sweat stain, tweed, seawater, etc., which is comparable to that of forbidden acid red 35 dye, thus can replace the forbidden acid red 35 dye, and the compatibility and synchronization of the dye with acid blue and acid yellow are poor.

Therefore, it is necessary to develop a red dye with a blue color, which can be matched with blue and yellow to obtain a bright dye with various color fastness.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide an acid red dye and a preparation method and application thereof, and particularly provides the acid red dye for fur and the preparation method and application thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides an acid red dye for furs (herein designated as acid red HFR), wherein the chemical structure of the acid red dye for furs is shown as formula (i):

the invention develops a brand-new acid red dye with the structure as shown in the specification, the dye has good compatibility with other dyes such as acid blue and acid yellow, has good level-dyeing property, has excellent fastness indexes such as perspiration fastness, light fastness, dry and wet rubbing fastness and washing fastness, and is very suitable for dyeing fur.

In a second aspect, the present invention provides a process for producing acid red dye for fur according to the first aspect, the process comprising the steps of:

reacting a compound (white solid) shown in a formula (II) and a compound (light gray solid) shown in a formula (III) serving as raw materials under the catalysis of a catalyst to obtain an acid red dye (red solid) for fur shown in a formula (I);

the preparation method of the acid red dye for fur (named acid red HFR in the invention) is simple and easy to operate, is very suitable for large-scale industrial production, and has good practicability. The acid red dye for fur prepared by the method has high yield and purity.

Preferably, the preparation method comprises the following steps:

(1) Mixing a compound shown in a formula (II) with water, heating and preserving heat;

(2) Adding a compound shown as a formula (III) into the product obtained in the step (1), then adding a catalyst, adjusting the pH value, and reacting until the end point.

Preferably, the mass ratio of the compound represented by the formula (II) in the step (1) to water is 1 (50-300), for example, 1.

The mass ratio of the compound shown in the formula (II) to water is specially selected to be 1 (50-300) because if the using amount of water is relatively reduced, the purity and the yield are reduced, mainly the water amount is not enough and is difficult to filter, and a filter cake is difficult to wash; if the amount of water used is relatively excessive, the product yield is seriously affected.

Preferably, the temperature in step (1) is raised to 60-80 ℃, for example, 60 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃ or 80 ℃, etc., preferably 68-72 ℃, and other specific values in the numerical range can be selected, which is not described herein again.

Preferably, the heat preservation time in the step (1) is 40-80min, for example, 40min, 50min, 60min, 70min or 80min, and other specific values in the numerical range can be selected, which are not described herein again.

The heating and heat preservation treatment is to ensure that the compound shown in the formula (II) is fully pulped and has no obvious particles, so that the reaction is more complete, and the purity and yield of the reaction are improved.

Preferably, the compound shown in the formula (III) is added to the product in the step (1) in the step (2) for 25-35min, such as 25min, 28min, 30min, 32min or 35min, and the temperature is controlled at 60-80 ℃, such as 60 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃ or 80 ℃, and the like, preferably 68-72 ℃; other specific point values within the above numerical range can be selected, and are not described in detail herein.

The reason why the duration of adding the compound represented by the formula (III) to the product of the step (1) is 25 to 35min is that if the duration is further shortened, the dissolution effect of the compound represented by the formula (III) in the reaction system is affected, and the reaction effect is further affected.

Preferably, the mass ratio of the compound represented by the formula (iii) to the compound represented by the formula (ii) in the step (2) is (1.1-1.3): 1, for example, 1.1, 1.2, 1 or 1.3, and other specific values within the numerical range can be selected, and are not repeated here.

The mass ratio of the compound of the formula (III) to the compound of the formula (II) is specifically selected to be in the range of (1.1 to 1.3): 1 because if the relative amount of the compound of the formula (III) is further decreased, the reaction of the compound of the formula (II) is incomplete, resulting in an excessively low yield; if the relative amount of the compound represented by the formula (III) is further increased, more by-products are produced and the purity is not high.

Preferably, the catalyst of step (2) comprises ferrous chloride, iron powder, cuprous chloride or cuprous sulfate, preferably cuprous sulfate.

When the catalyst is cuprous sulfate, the time required by the reaction is shortest, and the reaction time required by the ferrous chloride, the iron powder and the cuprous chloride is 8h, 10h and 7h respectively; meanwhile, the yield and the purity of the reaction are also highest.

Preferably, the mass of the catalyst in the step (2) is 1-7% of the mass of the compound shown in the formula (II), for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, etc., and other specific values in the numerical range can be selected, which are not described in detail herein, and are preferably 3-5%.

The mass of the catalyst is 1-7% of that of the compound shown in the formula (II) because if the using amount of the catalyst is further reduced, the reaction time is prolonged to exceed 13h, and the time cost is consumed; if the amount of the catalyst is further increased, the formation of by-products is easily caused, and the purity of the dye is reduced.

Preferably, the pH value adjustment in the step (2) uses an alkaline solution.

Preferably, the alkaline solution comprises a sodium bicarbonate solution.

Preferably, the pH is adjusted to 7-8, for example, pH =7.0, pH =7.2, pH =7.5, pH =7.8, pH =8.0, and the like, and other specific values within the range of values may be selected, which is not described in detail herein.

The pH value is adjusted to 7-8 because the reaction time is prolonged due to further reduction of the pH value, and the purity and the yield are influenced; further increases in pH also affect purity and yield.

Preferably, the reaction in step (2) is carried out at 60-80 ℃, such as 60 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃ or 80 ℃, and other specific values in the numerical range can be selected, and are not described in detail herein, and 68-72 ℃ is preferred.

The reaction temperature is specifically selected to be 60-80 ℃, when the reaction temperature is further reduced, the reaction process is slow, the reaction time is long, more byproducts are obtained, the purity is not high, and the yield is too low; when the reaction temperature is too high, the solubility of the acid red HFR is too good, and the solubility in water is too high, resulting in too low a yield.

Preferably, the end of the reaction in step (2) is monitored by thin layer chromatography and the developing solvent comprises cyclohexane.

Preferably, the reaction in step (2) is terminated, and then is incubated at 68-72 deg.C (e.g., 68 deg.C, 69 deg.C, 70 deg.C, 71 deg.C, 72 deg.C, etc.) for 40-60min (e.g., 40min, 45min, 50min, 55min, 60min, etc.), filtered, and washed with 8-12% (e.g., 8%, 9%, 10%, 11%, 12%, etc.) aqueous sodium chloride solution.

As a preferred technical scheme of the invention, the preparation method of the acid red dye for fur comprises the following steps:

(1) Mixing a compound shown as a formula (II) with water according to a mass ratio of 1 (50-300), heating to 60-80 ℃, and preserving heat for 40-80min;

(2) Slowly adding the compound shown in the formula (III) into the product in the step (1) for 25-35min, and controlling the temperature at 60-80 ℃, wherein the mass ratio of the compound shown in the formula (III) to the compound shown in the formula (II) is (1.1-1.3): 1;

(3) Then adding a catalyst with the mass of 1-7% of the compound shown in the formula (II), adjusting the pH value to 7-8 by using 30% sodium bicarbonate solution, reacting at 60-80 ℃ until the end point, and monitoring by using a thin layer chromatography, wherein a developing agent comprises cyclohexane;

(4) And (3) after the reaction is finished, preserving the heat for 40-60min at 68-72 ℃, filtering, and washing with 8-12% sodium chloride aqueous solution to obtain the acid red dye for the fur.

In a third aspect, the present invention provides a use of the acid red dye for fur according to the first aspect, in dyeing fur, wherein the dye used for dyeing is a single acid red dye for fur according to the first aspect or a compound dye comprising the acid red dye for fur according to the first aspect.

In practical application, those skilled in the art can use the acid red dye of the present invention in combination with other dyes such as acid blue 25 and acid yellow 49 according to actual needs, and the acid red dye has good compatibility. The acid red dye of the present invention is excellent in perspiration fastness, light fastness, dry and wet rubbing fastness and washing fastness, whether used alone or in combination.

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

the invention develops a brand-new acid red dye (named acid red HFR in the invention), the dye has good compatibility and level-dyeing property with other dyes such as acid blue and acid yellow, and each fastness index such as perspiration fastness, light fastness, dry and wet rubbing fastness and washing fastness is excellent, so the dye is very suitable for dyeing fur. The preparation method of the acid red dye for fur is simple and easy to operate, is very suitable for large-scale industrial production, and has good practicability. The acid red dye for fur prepared by the method has high yield and high purity.

Drawings

FIG. 1 is a high performance liquid chromatogram of the acid red dye for fur prepared in example 3;

FIG. 2 is a high performance liquid chromatogram of the acid red dye for fur prepared in example 4.

Detailed Description

To further illustrate the technical means and effects of the present invention, the following further describes the technical solution of the present invention with reference to the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.

The compounds of formula (II) (HPLC ≥ 97%), the compounds of formula (III) (HPLC ≥ 99%), cuprous sulfate (HPLC ≥ 96%), ferrous chloride, iron powder, cuprous chloride, sodium bicarbonate (HPLC ≥ 98%), cyclohexane (analytically pure ≥ 99.99%) in the following examples were purchased from the alatin chemical reagent net.

The purity of the product was calculated in the following examples using a Shimadzu LC-10ATvp HPLC chromatograph with mobile phases: acetonitrile/water =65/35, flow rate 1.0mL/min, chromatography column model Thermo Scientific ^TM DNAPac ^TM RP HPLC column.

The compounds of formula (I), formula (II) and formula (III) referred to in the following examples are as follows:

example 1

This example provides an acid red dye for fur having the following structure, and the preparation method thereof is as follows:

(1) Mixing 4.5g of a compound shown as a formula (II) with water according to a mass ratio of 1;

(2) Slowly adding a compound shown in a formula (III) into the product in the step (1) for 30min, and controlling the temperature at 70 ℃, wherein the mass ratio of the compound shown in the formula (III) to the compound shown in the formula (II) is 1.2;

(3) Then cuprous sulfate with the mass of 3% of that of the compound shown in the formula (II) is added, the pH value is adjusted to 7.5 by using 30% sodium bicarbonate solution, the reaction is carried out at 70 ℃ until the end point, the monitoring is carried out by using thin layer chromatography, the developing agent is cyclohexane, and the reaction is completed within 5 hours;

(4) And (3) after the reaction is finished, preserving the temperature for 50min at 70 ℃, filtering, and washing by using 10% sodium chloride aqueous solution to obtain the acid red dye for fur. The purity and yield of the product were determined as shown in table 1.

Example 2

This example provides an acid red dye for fur which is constituted such that the temperature is raised to 20 ℃ in the step (1), the temperature in the step (2) is controlled to 20 ℃, the reaction temperature in the step (3) is 20 ℃ and the temperature in the step (4) is kept at 20 ℃, and the method for producing the acid red dye is different from that in the example 1. All other conditions were kept constant. The purity and yield of the product were determined as shown in table 1.

Example 3

This example provides an acid red dye for fur which is constituted such that the temperature is raised to 40 ℃ in the step (1), the temperature in the step (2) is controlled to 40 ℃, the reaction temperature in the step (3) is 40 ℃ and the temperature in the step (4) is kept at 40 ℃, and the method for producing the acid red dye is different from that in the example 1. All other conditions remained unchanged. The product was tested for purity and yield as shown in table 1. Its high performance liquid chromatography is shown in figure 1.

Example 4

This example provides an acid red dye for fur which is constituted such that the temperature is raised to 60 ℃ in the step (1), the temperature in the step (2) is controlled to 60 ℃, the reaction temperature in the step (3) is 60 ℃ and the temperature in the step (4) is maintained at 60 ℃, and which is different from the acid red dye of example 1. All other conditions were kept constant. The product was tested for purity and yield as shown in table 1. Its high performance liquid chromatography is shown in FIG. 2.

Example 5

This example provides an acid red dye for fur of the following constitution, which was prepared by a method different from that of example 1 only in that the temperature in step (1) was raised to 80 ℃, the temperature in step (2) was controlled to 80 ℃, the reaction temperature in step (3) was 80 ℃ and the temperature in step (4) was maintained at 80 ℃. All other conditions remained unchanged. The product was tested for purity and yield as shown in table 1.

Example 6

This example provides an acid red dye for fur which is constituted such that the temperature is raised to 90 ℃ in the step (1), the temperature in the step (2) is controlled to 90 ℃, the reaction temperature in the step (3) is 90 ℃ and the temperature in the step (4) is maintained at 90 ℃, and which is different from the acid red dye of example 1. All other conditions remained unchanged. The purity and yield of the product were determined as shown in table 1.

Examples 7 to 11

This example provides an acid red dye for fur of the following structure, which is prepared by a method different from example 1 only in that the mass ratio of the compound represented by formula (ii) to water in step (1) is 1. All other conditions remained unchanged. The product was tested for purity and yield as shown in table 1.

Examples 12 to 14

This example provides an acid red dye for fur with the following structure, and the preparation method is different from example 1 only in that the catalysts added in step (3) are ferrous chloride, iron powder and cuprous chloride in this order. All other conditions remained unchanged. The product was tested for purity and yield as shown in table 1.

Examples 15 to 17

This example provides an acid red dye for fur of the following structure, which was prepared by a method different from example 1 only in that the amounts of the catalysts added in step (3) were 1%, 5%, and 7% in this order. All other conditions remained unchanged. The purity and yield of the product were determined as shown in table 1.

Examples 18 to 21

This example provides an acid red dye for fur of the following structure, which is prepared by a process different from example 1 only in that the amount of the compound represented by the formula (ii) is kept constant, but the mass ratio of the compound represented by the formula (iii) to the compound represented by the formula (ii) is 0.97, 1.05, 1.30, 1.40. All other conditions remained unchanged. The product was tested for purity and yield as shown in table 1.

Examples 22 to 24

This example provides an acid red dye for fur of the following structure, which is prepared by a method different from example 1 only in that the pH is adjusted to 3.5, 5.5, 9.5 in order by using a 30% sodium bicarbonate solution in step (3). All other conditions remained unchanged. The purity and yield of the product were determined as shown in table 1.

Evaluation test:

(1) Product purity and yield are shown in table 1:

TABLE 1

From the data in table 1, it can be seen that: the preparation method of the acid red dye for fur, which is provided by the invention, has the advantages of high purity and high yield, and the purity and the yield of the product can be obviously influenced by the reaction temperature, the amount of water, the type of the catalyst, the amount of the catalyst, the mass ratio of the two raw materials and the pH value of a reaction system.

(2) Evaluation of fastness index

Three dyes were prepared, one of which was the acid red HFR of the present invention prepared in example 1 alone; the second is a compound dye formed by mixing acid red HFR, acid blue 25 and acid yellow 49 which are prepared in the embodiment 1 according to the mass ratio of 5; the third is a compound dye prepared by mixing the acid red HFR, the acid blue 25 and the acid yellow 49 according to the invention, which are prepared in the embodiment 1, according to the mass ratio of 10. The staining was performed according to the following procedure:

(2.1) selecting skins: selecting raw leather with clean fur, wherein the shrinkage temperature is more than or equal to 95 ℃;

(2.2) dyeing is carried out at a temperature of 70 ℃ in a bath ratio of 20:

(2.2.1) 0.8ml/L of fur leveling agent DL for 30min;

(2.2.2) acid Red HFR 0.5ml/L for 60min;

or silver gray (0.5 ml/L acid red HFR, 0.7ml/L acid blue 25, 0.8ml/L acid yellow 49) for 60min;

or wine red (1 ml/L acid red HFR, 0.1ml/L acid blue 25, 0.1ml/L acid yellow 49) for 60min;

(2.2.3) 1.0 ml/L85% formic acid, 60min;

(2.2.4) 1.0 ml/L85% formic acid, 30min;

(2.2.5) peeling, cleaning, spin-drying, drying and finishing.

Evaluating the obtained dyed leather by using four indexes of perspiration fastness, light fastness, dry and wet rubbing fastness and washing fastness, wherein the light fastness adopts Japanese standard JIS L0842-2008, and the highest level 5; the washing fastness is referenced to GB/T3921-2008; the dry and wet rubbing fastness is in reference to GB/T3922; perspiration fastness is referred to ISO 105e 04. The results are shown in table 2:

TABLE 2

Name of dye	Fastness to perspiration	Color fastness to sunlight	Dry and wet rubbing fastness	Fastness to washing
					Acid Red HFR	Grade 3-4	Grade 5	Grade 5	Grade 5
Silver ash	4 stage	4-5 stages	Grade 5	4-5 stages
					Wine red	Grade 4	4-5 stages	Grade 5	4-5 stages

As can be seen from the data in Table 2: the acid red dye has good fastness indexes no matter used alone or in combination.

The applicant states that the present invention is illustrated by the above examples to show the acid red dye for furs and the preparation method and application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

Claims

1. A preparation method of acid red dye for fur is characterized by comprising the following steps:

(1) Mixing the compound shown in the formula (II) with water, heating and preserving heat;

(2) Adding a compound shown as a formula (III) into a product obtained in the step (1), adding cuprous sulfate, wherein the mass of the cuprous sulfate is 3-5% of that of the compound shown as the formula (II), adjusting the pH value to 7-8, and reacting until the end point; the chemical structure of the acid red dye for fur is shown as the formula (I):

2. the process for producing acid red dye for fur use according to claim 1, wherein the mass ratio of the compound represented by the formula (II) in the step (1) to water is 1 (50-300).

3. The process for producing acid red dyes for furs according to claim 1, wherein the mass ratio of the compound represented by the formula (II) to water in the step (1) is 1 (80-230).

4. The process for producing acid red dyes for furs according to claim 1, wherein the temperature in the step (1) is raised to 60 to 80 ℃.

5. The process for producing acid red dyes for furs according to claim 1, wherein the temperature in the step (1) is raised to 68 to 72 ℃.

6. The process for producing acid red dye for fur according to claim 1, wherein the holding time in the step (1) is 40 to 80min.

7. The process for producing acid red dyes for furs according to claim 1, wherein the compound represented by the formula (III) is added to the product of the step (1) in the step (2) for a period of 25 to 35min at a temperature controlled in the range of 60 to 80 ℃.

8. The process for producing acid red dyes for fur use according to claim 1, wherein the compound represented by the formula (III) is added to the product of the step (1) in the step (2) for 25 to 35min at a temperature controlled in the range of 68 to 72 ℃.

9. The process for producing an acid red dye for fur according to claim 1, wherein the mass ratio of the compound represented by the formula (III) in the step (2) to the compound represented by the formula (II) is (1.1 to 1.3): 1.

10. The process for producing acid red dye for fur according to claim 1, wherein the pH adjustment in the step (2) is carried out using an alkaline solution.

11. The process for producing acid red dyes for furs according to claim 10, wherein the alkaline solution comprises sodium bicarbonate solution.

12. The process for producing acid red dye for fur according to claim 1, wherein the reaction in the step (2) is carried out at 60 to 80 ℃.

13. The process for producing acid red dyes for furs according to claim 1, wherein the reaction in step (2) is carried out at 68 to 72 ℃.

14. The process for producing an acid red dye for fur according to claim 1, wherein the end point of the reaction in the step (2) is monitored by thin layer chromatography, and the developing agent comprises cyclohexane.

15. The process for producing acid red dye for fur according to claim 1, wherein the reaction in the step (2) is terminated, and then the temperature is maintained at 68 to 72 ℃ for 40 to 60 minutes, filtered, and washed with 8 to 12% aqueous sodium chloride solution.

16. The use of the acid red dye for fur prepared by the process for preparing an acid red dye for fur according to claim 1 for dyeing fur, wherein in the use, the dye used for dyeing fur is a single acid red dye for fur or a combination dye including the acid red dye for fur.