Process for the preparation of an antigenic fibrillation cross-linker and uses thereof

Abstract

The application discloses a preparation method of an anti-fibrillation crosslinking agent and application thereof. The preparation method can be used for synthesizing under anhydrous condition, avoids hydrolysis in the synthesis process, and has the advantages of few synthesis steps and no need of post-treatment. The preparation method is suitable for silk or lyocell fabrics, can improve the anti-fibrillation capacity of the fabrics, and does not cause competitive adsorption with active dyes when the fabrics are dyed, and has little influence on the color and color change of the fabrics.

Description

Technical Field

[0001] This invention belongs to the field of textile auxiliaries, specifically relating to a method for preparing an antigen-based fiber-crosslinking agent and its application. Background Technology

[0002] When fabrics are subjected to various dry and wet frictions during use and machine washing, the fibrils inside the fibers are easily separated and become fibrillated, resulting in a whitening or graying appearance.

[0003] Triazine crosslinking agents are an important means of solving the problems of whitening and graying in fabrics. The cyanuric chloride structural unit contains active chlorine, and the active chlorine in a cyanuric chloride derivative molecule can react with the amino and hydroxyl groups on the fabric fibers to form a crosslinking reaction. Thus, the cyanuric chloride derivative acts as a bridge, crosslinking the amino and hydroxyl groups on the fabric fibers together to obtain a crosslinked product, thereby improving the fabric's anti-fibrillation ability and preventing graying. For example, patent publication number WO 99 / 19555A reports a substituted dichlorotriazine crosslinking agent, preferably sodium 2,4-dichloro-6-hydroxytriazine, which has good anti-fibrillation performance. However, this type of crosslinking agent has a high water content, requires a large amount, is not suitable for long-term storage, is prone to hydrolysis, and is unstable in acids. Patent CN117758512A uses multifunctional triazine compounds as crosslinking agents to finish lyocell fabrics through a cold pad-batch process. This shortens the processing flow, reduces mechanical friction between the fabric and equipment, and lowers the tendency for fibrillation. However, the synthesis of this crosslinking agent is cumbersome, and the crosslinking agent emulsion is prone to hydrolysis, making it unsuitable for long-term storage. Chinese patent CN115897233A discloses a treatment for preventing ash damage to silk fabrics. This involves immersing the silk fabric in an anti-ash damage agent solution to obtain an anti-ash damage silk fabric. However, the synthesis of this anti-ash damage agent solution is cumbersome, produces hydrolysis byproducts, and the resulting product is an aqueous powder. Furthermore, the chlorinated triazine compounds are prone to hydrolysis, therefore, drying is necessary for storage, and the product is dissolved before use.

[0004] To address the issue of easy hydrolysis of crosslinking agent emulsions during room temperature storage, current technologies typically involve freeze-drying or spray-drying the emulsions for storage in powder form, which is then dissolved before use. Freeze-drying or spray-drying requires complex equipment and is time-consuming and energy-intensive. Summary of the Invention

[0005] To address the shortcomings of the aforementioned cyanuric chloride derivative crosslinking agents, such as easy hydrolysis, instability, and difficulty in long-term storage, this invention proposes a preparation method. This method can be synthesized under anhydrous conditions, avoiding hydrolysis during the synthesis process, and also has the advantages of fewer synthesis steps and no need for post-processing.

[0006] One of the technical solutions of this invention is to provide a method for preparing an antigen-fibrillating crosslinking agent: cyanuric chloride and a water-soluble liquid-phase organic compound are subjected to a substitution reaction under anhydrous alkaline conditions, causing the water-soluble liquid-phase organic compound to replace one of the Cl atoms on the cyanuric chloride. The water-soluble liquid-phase organic compound serves as both the reactant and the solvent, eliminating the need for water as a solvent to achieve the Cl substitution reaction. The resulting cyanuric chloride derivative is a liquid and requires no filtration or freeze-drying; it can be stored directly at room temperature for later use. Because the crosslinking agent contains very little water, hydrolysis of the crosslinking agent is avoided.

[0007] In a preferred embodiment, the water-soluble organic compound in the liquid phase is a non-ionic organic compound, which ensures that the crosslinking agent has good solubility in water and does not compete with the reactive dye for adsorption during fabric dyeing, thus having little impact on the color change of the fabric.

[0008] In some embodiments of the present invention, the liquid-phase water-soluble organic compound includes one or more of ethylene glycol, diethylene glycol, diethylene glycol methyl ether, aminoethanol, glycerol, polyethylene glycol, polypropylene glycol, polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, and polyetheramine.

[0009] In some embodiments of the present invention, under conditions of 0-5°C, a liquid-phase water-soluble organic compound, cyanuric chloride and an alkali (triethylamine) in a molar ratio of 1:1:1 are added to a reaction apparatus and reacted for 6 hours to obtain a cyanuric chloride derivative.

[0010] The second technical solution of the present invention is to provide an antigen-fibrillating crosslinking agent, the structure of which is as follows:

[0011]

[0012] X is one of F and Cl;

[0013] R contains a water-soluble group and can be formed by dehydrogenation of one of the following: ethylene glycol, diethylene glycol, diethylene glycol methyl ether, aminoethanol, glycerol, polyethylene glycol, polypropylene glycol, polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, or polyetheramine. For example, R formed by dehydrogenation of ethylene glycol and substitution with Cl is -OCCOH, and the structural formula of the antigen fibrinolytic crosslinking agent is:

[0014] .

[0015] The R formed by dehydrogenation of diethylene glycol and substitution with Cl is -OCH2CH2OCH2CH2OH. The structural formula of the antigen fibrinolytic crosslinking agent is:

[0016] .

[0017] The R formed by substitution of polypropylene glycol (n=10) with Cl is -(OC3H6). 10The structural formula of the antigen-fibrillating cross-linking agent is:

[0018] .

[0019] The R formed by dehydrogenation and Cl substitution of polyethylene glycol monomethyl ether (n=8) is -(OC2H4)8OCH3. The structural formula of the antigen fibrinolytic crosslinking agent is:

[0020] .

[0021] The third technical solution of this invention is to provide an application of an antigen-fibrillating crosslinking agent in the field of fabric anti-gray damage. The specific operation steps are as follows: dyeing and crosslinking in the same bath with a bath ratio of 1:4-20, adding 5-10 g / L of crosslinking agent to the fabric and running it evenly, adding reactive dye and running it evenly, adding 40-60 g / L of sodium sulfate and continuing to run it for 20 minutes, raising the temperature to 60-80℃, adding 20-30 g / L of soda ash and continuing to run it for 30-60 minutes, removing it from the bath, washing it with water, neutralizing it, and drying it to produce anti-gray damage silk fabric.

[0022] The crosslinking agent is a dichlorotriazine crosslinking agent, which contains two active groups (Cl) that can react with the amine and hydroxyl groups of silk fibers, thereby locking between the fiber chains, enhancing the transverse forces between fibroin fibers, and preventing gray damage.

[0023] Meanwhile, this crosslinking agent contains a nonionic, water-soluble group (R), enabling it to dissolve in water and penetrate the silk fibroin fibers to undergo crosslinking. When dyeing silk fabrics, reactive dyes are typically anionic, and since this crosslinking agent is nonionic, it does not affect the adsorption and color development of the reactive dyes.

[0024] The technical effects of this invention are as follows:

[0025] 1) Using nonionic organic compounds as reaction raw materials can serve as both reactants and solvents, thus avoiding hydrolysis during the reaction process.

[0026] 2) The product prepared by this invention is a liquid, which does not require filtration, freeze drying or other treatments. It is simple to operate and easy to store.

[0027] 3) The water-soluble compound used in this invention is non-ionic, which ensures that the crosslinking agent has good solubility in water and does not compete with the reactive dye for adsorption during fabric dyeing, thus having little impact on the color change of the fabric. Attached Figure Description

[0028] Figure 1 Microscopic image of silk fabric after 5 washes without crosslinking agent;

[0029] Figure 2 Microscopic image of silk fabric after 5 washes with water under 5 g / L crosslinking agent conditions;

[0030] Figure 3 Microscopic image of silk fabric after 5 washes with water under 10 g / L crosslinking agent conditions;

[0031] Figure 4 SEM images of Lyocell fabric after 5 washes without crosslinking agent;

[0032] Figure 5 SEM images of Lyocell fabric after 5 washes with water under 2 g / L crosslinking agent conditions;

[0033] Figure 6 SEM images of Lyocell fabric after 5 washes with water under 3g / L crosslinking agent conditions;

[0034] Figure 7 SEM images of Lyocell fabric after 5 washes with water under 4 g / L crosslinking agent conditions;

[0035] Figure 8 SEM image of Lyocell fabric after 5 washes with water under 5 g / L crosslinking agent conditions. Detailed Implementation

[0036] The following examples are provided to further illustrate the present invention and are intended to explain the invention, not to limit its scope. Unless otherwise specified, all figures are expressed in parts by weight and weight percentages.

[0037] Unless otherwise specified, the raw materials used in this invention are all conventional commercially available products; unless otherwise specified, the methods used in this invention are all conventional methods in the field.

[0038] The dyeing and crosslinking process described in this invention is a common dyeing process. "Dyeing and crosslinking" means that the conventional dyeing process is not changed, but only an additional crosslinking agent is added.

[0039] The crosslinking agent concentration mentioned in this invention is the concentration of the crosslinking agent in the bath. For example, a crosslinking agent concentration of 5-10 g / L means adding 5-10 g of crosslinking agent to a 1 L dyeing bath.

[0040] The liquor ratio mentioned in this invention refers to the ratio of fabric to dyeing bath. For example, a liquor ratio of 1:10-20 means 10g of fabric and 100-200g of dyeing bath.

[0041] The embodiments of the present invention will be further described below with reference to several examples.

[0042] It should be understood that the described embodiments are merely some, not all, of the embodiments in this application. All other embodiments obtained by those skilled in the art based on the embodiments in this application without inventive effort are within the scope of protection of this application.

[0043] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms “a,” “the,” and “the” used in the embodiments of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0044] Example 1

[0045] At 0°C, polyethylene glycol 400, cyanuric chloride and alkali (triethylamine) in a molar ratio of 1:1:1 were added to the reaction apparatus and reacted for 6 hours to obtain an antigen-fibrillating crosslinking agent.

[0046] The anti-grinding effect of the antigen-fibrillating crosslinking agent prepared in this embodiment was tested using silk fabric as the target material. The specific operation is as follows:

[0047] The dyeing and crosslinking process is carried out in the same bath with a bath ratio of 1:20. 10 g / L of crosslinking agent is added to the silk fabric and the mixture is stirred evenly. Then, reactive dye is added and stirred evenly. 40 g / L of sodium sulfate is added and the mixture is stirred for another 20 minutes. The temperature is raised to 80℃ and 20 g / L of soda ash is added and the mixture is stirred for another 60 minutes. The fabric is then removed from the bath, washed with water, neutralized, and dried to produce a silk fabric resistant to gray damage.

[0048] Evaluation method for preventing graying: Refer to standard AATCC 135, use a standard washing machine, wash 5 times, remove, dry, and observe the graying condition of the fabric surface under a microscope. Figures 1-3 .

[0049] Dyeing evaluation method: A colorimeter is used to test the dyeing condition of the fabric, and the degree of color depth is expressed in the form of K / S value.

[0050] Gray stain resistance: Gray stain resistance is divided into 5 levels: Level 5 (no gray stain), Level 4 (very slight gray stain), Level 3 (slight gray stain), Level 2 (moderate gray stain), and Level 1 (severe gray stain).

[0051] As shown in Table 1, the crosslinking agent of the present invention, at a dosage of 10 g / L, can achieve a level 4 anti-gray damage effect on the treated silk fabric.

[0052] As shown in Table 2, the crosslinking agent of the present invention can be used in the same bath as the dyeing of silk fabrics, with little impact on the dyeing performance of the fabrics.

[0053]

[0054] Example 2

[0055] At 5°C, polyethylene glycol monomethyl ether 350, cyanuric chloride and alkali (triethylamine) in a molar ratio of 1:1:1 were added to the reaction apparatus and reacted for 6 hours to obtain an antigen-fibrillating crosslinking agent.

[0056] The anti-grinding effect of the antigen-fibrillating crosslinking agent prepared in this embodiment was tested using Lyocell fabric as the target material. The specific operation is as follows:

[0057] Crosslinking in the same bath with a bath ratio of 1:10 is used. After pretreatment, 5 g / L of crosslinking agent is added and the mixture is stirred evenly. Then, 3% Reactive Red 3BS dye is added and stirred evenly. Finally, 60 g / L of sodium sulfate is added and the mixture is stirred for 20 minutes. The temperature is raised to 60℃, and 30 g / L of soda ash is added and the mixture is stirred for 30 minutes. The mixture is then removed from the bath, washed with water, neutralized, and dried to obtain antigen-fibrillated Lyocell fabric.

[0058] Evaluation method for antigen fibrillation: Following standard AATCC 135, the fabric was washed 5 times in a standard washing machine, removed, dried, and the fibrillation status was observed using a scanning electron microscope. The antigen fibrillation effect was classified into 5 grades: Grade 5 (no fibrillation), Grade 4 (very slight fibrillation), Grade 3 (slight fibrillation), Grade 2 (moderate fibrillation), and Grade 1 (severe fibrillation).

[0059] The staining evaluation method is as described in Example 1.

[0060] As shown in Table 3, in this embodiment, with a crosslinking agent dosage of 5 g / L, the antigen-fibrillation effect of the treated Lyocell fabric can reach level 5.

[0061] As shown in Table 4, the crosslinking agent of the present invention has no effect on the dyeing performance of the fabric.

[0062]

[0063] The above embodiments describe in detail the structure, features, and effects of the present invention. The above description is only a preferred embodiment of the present invention. Any changes made in accordance with the concept of the present invention, or equivalent embodiments modified to have equivalent changes, shall still fall within the scope of protection of the present invention if they do not exceed the scope covered by the specification.

[0064] Although embodiments of the invention have been disclosed for illustrative purposes, those skilled in the art will understand that various substitutions, variations, and modifications are possible without departing from the spirit and scope of the invention and the appended claims. Therefore, the scope of the invention is not limited to the contents disclosed in the embodiments.

Claims

1. The application of antigen-fibrillating crosslinking agent in the field of fabric anti-grinding, wherein the antigen-fibrillating crosslinking agent has the following structure: X is Cl; R is polyethylene glycol or polyethylene glycol monomethyl ether.

2. The application according to claim 1, characterized in that, The fabric is made of silk or lyocell.

3. The application according to claim 1, characterized in that, The antigen fibrinolytic crosslinking agent is prepared by the following method: A substitution reaction is carried out between cyanuric chloride and a water-soluble liquid-phase organic compound under anhydrous alkaline conditions, such that the water-soluble liquid-phase organic compound replaces one of the Cl groups on the cyanuric chloride; the water-soluble liquid-phase organic compound is polyethylene glycol or polyethylene glycol monomethyl ether.

4. The application according to claim 3, characterized in that, Triethylamine is added to form the alkaline conditions described above.

5. The application according to claim 4, characterized in that, The molar ratio of the liquid-phase water-soluble organic compound, cyanuric chloride, and triethylamine was 1:1:1, the reaction temperature was 0-5℃, and the reaction time was 6h.

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