Bisphenol-free acidic color fixing agent based on plant extract and preparation method thereof

Abstract

The invention discloses a plant extract-based bisphenol-free acidic color fixing agent and a preparation method thereof, the color fixing agent adopts natural plant polyphenol as a raw material, the use of bisphenol compounds as a raw material is avoided, and bisphenol substances may induce an oxidative stress system of a human body, disturb an endocrine system and an immune system or cause in-vivo balance disorder, so that the color fixing agent has a good color fixing effect. Even the risk of increasing diabetes and heart disease is caused, and even certain reproductive toxicity is caused. The plant polyphenol compound used for preparing the color fixing agent is non-toxic and harmless, and no toxic substance is left in the color fixing agent finished product. The water-soaking-resistant color fastness and the soaping-resistant color fastness of the bisphenol-free acidic color fixing agent can be both improved to level 3 or above.

Description

Technical Field

[0001] The invention relates to the technical field of color fixing agents, in particular to a bisphenol-free acidic color fixing agent based on plant extracts and a preparation method thereof. Background Art

[0002] Nylon fiber has many characteristics such as high strength, good abrasion resistance and resilience, and excellent chemical stability, so it is widely used in the textile industry. In actual production, acid dyes are often used to dye nylon, but when dyeing dark colors or using a large amount of dye, there are many dyes that are not completely fixed to the fiber and are easy to fall off the fiber, showing poor soap fastness and water fastness, which is difficult to meet market requirements. Therefore, acid dye fixing agents must be used to further fix the dyes that are not completely combined with the fiber and improve their color fastness.

[0003] Although the color fixing agents currently available on the market have good color fixing effects, there are problems with excessive levels of phenol, bisphenol F, and bisphenol S. The color fixing agents for acid dyes are mainly composed of sulfonates of phenol formaldehyde polymers or formaldehyde polymers of bisphenol sulfonates, and during the sulfonation process with concentrated sulfuric acid, the phenolic resin will partially depolymerize to release phenol and formaldehyde. Consumer products containing bisphenols will inevitably be released into the environment, which may pose a potential threat to animals and humans. Summary of the invention

[0004] The present invention aims at the problem that the current color fixing agent has excessive phenol and bisphenol, and proposes a bisphenol-free acidic color fixing agent based on plant extracts and a preparation method thereof. The present invention uses chlorinated benzene compounds and natural plant polyphenols as reaction raw materials, utilizes the active groups of the chlorinated benzene compounds to react with the active hydrogen of the plant polyphenols, and controls the molecular weight by regulating the molar ratio, thereby avoiding the problem that the molecular weight after polymerization is too large due to the excessive number of phenolic hydroxyl groups of the plant polyphenols, the reaction activity is too high, and the molecular weight exceeds the molecular weight range of the color fixing agent. The color fixing agent controls the proportion of raw materials during the synthesis process, so that no toxic substances remain in the product. The prepared color fixing agent can improve the color fastness to blistering and the color fastness to soaping to above level 3.

[0005] One of the technical solutions of the present invention is to provide a method for preparing a bisphenol-free acidic color fixing agent based on plant extracts, which specifically comprises the following steps: dissolving a plant polyphenol compound and a chlorobenzene-containing compound in a mixed solution of an organic solvent and water in a volume ratio of (1-4):1, heating and stirring, collecting the product by suction filtration, drying to remove the solvent, dissolving the product in glacial acetic acid, and adding concentrated sulfuric acid dropwise for sulfonation.

[0006] Furthermore, the molar ratio of the plant polyphenol compound to the chlorinated benzene compound is (1-4):1.

[0007] Furthermore, the heating and stirring temperature is 40-60° C., and the reaction time is 2-6 hours.

[0008] Furthermore, the temperature of the high temperature reaction is 100-105° C., and the reaction time is 2-3 hours.

[0009] Furthermore, the plant polyphenol compound includes one of gallic acid, coumaric acid, caffeic acid, ferulic acid, and protocatechuic acid, and the molecular weight of the plant polyphenol compound is between 100 and 3000. The surface of natural plant polyphenols has abundant hydroxyl and carboxyl groups and has high reactivity.

[0010] Furthermore, the chlorinated benzene compound includes one of p-dichlorobenzyl, o-dichlorobenzyl, m-dichlorobenzyl, benzyl chloride, benzyl trichloride, and 2-chlorophenol.

[0011] Furthermore, the molar ratio of the concentrated sulfuric acid to the chlorinated benzene compound is 1:(2-4).

[0012] Furthermore, the organic solvent includes one of acetone, tetrahydrofuran and butanone.

[0013] Furthermore, the volume ratio of the organic solvent to water is (1-4):1.

[0014] Furthermore, the drying condition is a vacuum oven at 55-60°C.

[0015] In some embodiments of the present invention, gallic acid and p-dichlorobenzyl are used as reaction raw materials, acetone is used as solvent, and the reaction formula is as follows: ; .

[0016] As described above, the carboxyl and hydroxyl groups on plant polyphenols can react with chlorinated benzene compounds. When the molar ratio of plant polyphenol compounds to chlorinated benzene compounds is (1-4):1, the plant polyphenols are in excess, which can ensure the complete reaction of chlorinated benzene compounds. Moreover, chlorinated benzene compounds are hydrolyzable, so the finished product will not contain chlorinated benzene compounds.

[0017] The second technical solution of the present invention is to provide a bisphenol-free acidic color fixing agent prepared by the above preparation method.

[0018] Beneficial effects of the present invention: 1. The present invention adopts a new synthetic route for color fixing agent, which is suitable for safe natural plant polyphenols, without using raw materials such as phenol, bisphenols, formaldehyde, etc., and will not cause the residue of the above toxic substances.

[0019] 2. The color fastness to blistering and the color fastness to soaping of the color fixing agent prepared by the present invention can be improved to above level 3. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is the appearance of the aqueous solution of Example 1; Figure 2 The blister fastness test results of Examples 1-4 are as follows; Figure 3 The following are the test results of color fastness to washing of Examples 1-4. DETAILED DESCRIPTION

[0021] The following examples are used to further illustrate the present invention, and their purpose is to illustrate the present invention and should not be construed as limiting the scope of the present invention. Unless otherwise specified, all parts by weight and weight percentages are used below.

[0022] It should be clear that the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present application.

[0023] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings.

[0024] In the present invention, the concentrated sulfuric acid is commercially available concentrated sulfuric acid, and generally, the concentration is not less than 98%.

[0025] In the present invention, the glacial acetic acid is commercially available glacial acetic acid, and generally, the concentration is not less than 99%.

[0026] The water fastness of the present invention is tested by water immersion for 5 minutes at 60° C. with a washing powder of 2.0 g / L. The lighter the color, the better the fastness.

[0027] The color fastness to washing described in the present invention is implemented in accordance with GB / T 3921-2008.

[0028] Example 1 Step 1: Gallic acid and benzyl dichloride were added to a four-necked flask at a molar ratio of 1:1, and a mixed solvent of acetone and water at a volume ratio of 1:1 was added to dissolve them. The mixture was stirred at 40°C for 4 hours.

[0029] Step 2: Collect the reaction product by suction filtration, dry it in a vacuum oven at 55°C to remove the solvent, and then redissolve it in glacial acetic acid. Raise the temperature to 100°C, add a small amount of concentrated sulfuric acid and stir for 3 hours. The molar amount of concentrated sulfuric acid is 1 / 2 of that of p-dichlorobenzyl, and the plant-based bisphenol-free color fixing agent can be obtained. The appearance of its aqueous solution is as follows Figure 1 shown.

[0030] The prepared plant-based bisphenol-free fixing agent was impregnated onto nylon fabric, and the blister fastness and soap washing fastness of the nylon fabric were tested. The test results were: blister fastness level 4, and color fastness to soap washing level 4.

[0031] Example 2 Step 1: Add coumaric acid and o-dibenzyl chloride in a molar ratio of 4:1 into a four-necked flask, add a mixed solvent of acetone and water in a volume ratio of 4:1 to dissolve them, and stir the mixture at 60°C for 2 hours.

[0032] Step 2: Collect the obtained reaction product by suction filtration, dry it in a vacuum oven at 60°C to remove the solvent, and then redissolve it in glacial acetic acid. Raise the temperature to 105°C, drop a small amount of concentrated sulfuric acid, and stir and react for 2 hours. The molar amount of concentrated sulfuric acid is 1 / 4 of that of p-dichlorobenzyl, and a plant-based bisphenol-free color fixing agent can be obtained.

[0033] The prepared plant-based bisphenol-free fixing agent was impregnated onto nylon fabric, and the blister fastness and soap washing fastness of the nylon fabric were tested. The test results were: blister fastness level 3, and color fastness to soap washing level 4.

[0034] Example 3 Step 1: Add caffeic acid and benzyl dichloride in a molar ratio of 3:1 into a four-necked flask, and add a mixed solvent of butanone and water in a volume ratio of 2:1 to dissolve them. Stir and react at 50°C for 6 hours.

[0035] Step 2: Collect the obtained reaction product by suction filtration, dry it in a vacuum oven at 55°C to remove the solvent, and then redissolve it in glacial acetic acid. Raise the temperature to 102°C, drop a small amount of concentrated sulfuric acid, and stir and react for 2.5 hours. The molar amount of concentrated sulfuric acid is 1 / 3 of that of p-dichlorobenzyl, and a plant-based bisphenol-free color fixing agent can be obtained.

[0036] The prepared plant-based bisphenol-free fixing agent was impregnated onto nylon fabric, and the blister fastness and soap washing fastness of the nylon fabric were tested. The test results showed that the blister fastness was level 3, and the color fastness to soap washing was level 3.5.

[0037] Example 4 Step 1: Ferulic acid and benzyl chloride are added to a four-necked flask at a molar ratio of 2:1, and a mixed solvent of tetrahydrofuran and water at a volume ratio of 3:1 is added to dissolve the mixture. The mixture is stirred at 50°C for 6 hours.

[0038] Step 2: Collect the obtained reaction product by suction filtration, dry it in a vacuum oven at 57°C to remove the solvent, and then redissolve it in glacial acetic acid. Raise the temperature to 102°C, drop a small amount of concentrated sulfuric acid, and stir and react for 2.5 hours. The molar amount of concentrated sulfuric acid is 1 / 2 of that of p-dichlorobenzyl, and a plant-based bisphenol-free color fixing agent can be obtained.

[0039] The prepared plant-based bisphenol-free fixing agent was impregnated onto nylon fabric, and the blister fastness and soap washing fastness of the nylon fabric were tested. The test results showed that the blister fastness was level 3.5, and the color fastness to soap washing was level 4.

[0040] Example 5 Step 1: Add protocatechuic acid and benzyl trichloride in a molar ratio of 3:1 into a four-necked flask, and add a mixed solvent of tetrahydrofuran and water in a volume ratio of 1:1 to dissolve them. Stir and react at 60°C for 4 hours.

[0041] Step 2: Collect the obtained reaction product by suction filtration, dry it in a vacuum oven at 55°C to remove the solvent, and then redissolve it in glacial acetic acid. Raise the temperature to 100°C, drop a small amount of concentrated sulfuric acid, and stir and react for 3 hours. The molar amount of concentrated sulfuric acid is 1 / 4 of that of p-dichlorobenzyl, and a plant-based bisphenol-free color fixing agent can be obtained.

[0042] Example 6 Step 1: Gallic acid and 2-chlorophenol were added to a four-necked flask at a molar ratio of 3:1, and a mixed solvent of tetrahydrofuran and water at a volume ratio of 2:1 was added to dissolve them. The mixture was stirred at 55°C for 4 hours.

[0043] Step 2: Collect the obtained reaction product by suction filtration, dry it in a vacuum oven at 60°C to remove the solvent, and then redissolve it in glacial acetic acid. Raise the temperature to 105°C, drop a small amount of concentrated sulfuric acid, and stir and react for 3 hours. The molar amount of concentrated sulfuric acid is 1 / 3 of that of p-dichlorobenzyl, and a plant-based bisphenol-free color fixing agent can be obtained.

[0044] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that gallic acid is replaced by phenol and the reaction molar ratio is controlled to be 2:1.

[0045] After replacing gallic acid with phenol, the molecular weight of the prepared product was only 290, and the molecular weight after sulfonation was only 370, with no color fixation effect. After impregnation treatment on nylon fabric, the blister fastness and soap fastness of nylon fabric were tested. The test results were: blister fastness 1.5 level, soap fastness 1.5 level.

[0046] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that p-dichlorobenzyl is replaced by paraformaldehyde. The specific operation is as follows:

[0047] Step 1: Gallic acid is added to a four-necked flask, deionized water is added, the temperature is raised to 90° C., a certain amount of paraformaldehyde is added in batches, the molar ratio of formaldehyde to gallic acid in the paraformaldehyde is controlled at 1.1 to 1.5, and the reaction is carried out at a constant temperature for 4 hours.

[0048] Step 2: Collect the reaction product by suction filtration, dry it in a vacuum oven at 55°C to remove the solvent, and then redissolve it in glacial acetic acid. Raise the temperature to 105°C, add a small amount of concentrated sulfuric acid and stir for 3 hours. The molar amount of concentrated sulfuric acid is 1 / 2 of that of gallic acid. The final product is insoluble in water and cannot be used as a color fixing agent.

[0049] Although the embodiments of the present invention are disclosed for illustrative purposes, those skilled in the art will appreciate that various substitutions, changes and modifications are possible without departing from the spirit and scope of the present invention and the appended claims. Therefore, the scope of the present invention is not limited to the contents disclosed in the embodiments.

Claims

1. A method for preparing a bisphenol-free acidic color fixing agent based on plant extracts, characterized in that: The method comprises the following steps: dissolving a plant polyphenol compound and a chlorobenzene-containing compound in a molar ratio of (1-4):1 in a mixed solution in which an organic solvent and water have a volume ratio of (1-4):1, heating and stirring, collecting the product by suction filtration, drying to remove the solvent, dissolving the product in glacial acetic acid, and dropping concentrated sulfuric acid for sulfonation.

2. The preparation method according to claim 1, characterized in that: The heating and stirring temperature is 40-60° C., and the reaction time is 2-6 hours.

3. The preparation method according to claim 1, characterized in that: The sulfonation was completed by stirring at 100-105°C for 2-3 hours.

4. The preparation method according to claim 1, characterized in that: The plant polyphenol compound includes one of gallic acid, coumaric acid, caffeic acid, ferulic acid and protocatechuic acid.

5. The preparation method according to claim 1, characterized in that: The chlorinated benzene compound includes one of p-dichlorobenzyl, o-dichlorobenzyl, m-dichlorobenzyl, benzyl chloride, benzyl trichloride and 2-chlorophenol.

6. The preparation method according to claim 1, characterized in that: The organic solvent includes one of acetone, tetrahydrofuran and butanone.

7. The preparation method according to claim 1, characterized in that: The molar ratio of the concentrated sulfuric acid to the chlorinated benzene compound is 1:(2-4).

8. The preparation method according to claim 1, characterized in that: The drying condition is a vacuum oven at 55-60°C.

9. A bisphenol-free acidic color fixing agent prepared by the preparation method as claimed in claim 1.

Images