Heat-resistant phenolic yellowing-resistant agent as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of textile, and particularly discloses a heat-resistant phenol-yellowing-resistant agent as well as a preparation method and application thereof. The heat-resistant phenolic yellowing-resistant agent comprises the following raw material components in parts by weight: 10-20 parts of fatty acid dihydrazide, 5-10 parts of fatty alcohol-polyoxyethylene ether carboxylic acid, 2-5 parts of a surfactant and 65-83 parts of deionized water. Fatty acid dihydrazide can capture free radicals and terminate an oxidation reaction chain, so that the fabric is protected from oxidative damage, and thermal yellowing and phenolic yellowing are prevented; the molecular structure of fatty alcohol-polyoxyethylene ether carboxylic acid contains hydrophilic groups and hydrophobic groups at the same time, so that a layer of protective film can be accurately formed on the surface of the fabric, substances causing thermal yellowing and phenolic yellowing are effectively isolated, and oxidation of phenolic substances is inhibited. Fatty acid dihydrazide is combined with carboxylic acid groups of fatty alcohol-polyoxyethylene ether carboxylic acid through hydrogen bonds or ionic bonds to form a compound, and thermal yellowing resistance, phenolic yellowing resistance, washability and stability of the fabric can be improved at the same time.

Description

Technical Field

[0001] The invention belongs to the field of textile technology, and specifically relates to a heat-resistant and phenol-resistant yellowing agent and a preparation method and application thereof. Background Art

[0002] In the textile industry, the color stability of fabrics is a key factor affecting their quality and market competitiveness. As consumers' requirements for the appearance quality and durability of textiles continue to increase, the problem of thermal yellowing and phenolic yellowing of fabrics during storage and use has received increasing attention.

[0003] Thermal yellowing is usually caused by changes in the chemical structure of the fabric when the fabric is stored or transported in a high temperature environment, such as in hot climates, or during processing such as high-temperature ironing, which causes yellowing. This not only seriously affects the color and appearance of the fabric, but may also reduce its commercial value and lead to a decrease in consumer satisfaction. Phenolic yellowing is caused by chemical reactions when the fabric comes into contact with phenolic antioxidants, nitrogen oxides and other substances in the environment, causing yellowing. This phenomenon is particularly common in cotton fabrics, as the special structure of cotton fibers makes it easier for them to react with these substances. Phenolic yellowing not only destroys the original color of the fabric, but may also affect its dyeing uniformity, making subsequent printing and dyeing processing more difficult.

[0004] At present, most of the existing anti-yellowing agents have technical problems such as single performance, poor anti-yellowing effect, and negative impact on the original performance of fabrics. For example, some anti-yellowing agents can only play a role in one of the situations of thermal yellowing or phenolic yellowing, and cannot solve the two yellowing problems at the same time; some anti-yellowing agents have unsatisfactory anti-yellowing effects in actual applications and cannot effectively inhibit the yellowing of fabrics; and some anti-yellowing agents will have a negative impact on the original performance of fabrics, such as strength and color fastness, during use, resulting in the reduction of other important performances of fabrics while solving the yellowing problem, which is still difficult to meet the actual needs of the market.

[0005] Therefore, the development of an anti-heat and anti-phenolic yellowing agent that can effectively resist both thermal yellowing and phenolic yellowing without damaging the original properties of the fabric is of vital importance to improving the quality of textile products and expanding the scope of market application. It is also a key technical problem that needs to be urgently solved in the current field of textile auxiliaries. Summary of the invention

[0006] The present invention aims to solve the technical problems of thermal yellowing and phenolic yellowing faced by fabrics during storage and use. To this end, the present invention proposes a heat-resistant and phenolic yellowing agent and a preparation method and application thereof, which has excellent resistance to thermal yellowing and phenolic yellowing while ensuring that the original properties of the fabrics are not damaged.

[0007] The inventive concept of the present invention is as follows: The heat and phenol yellowing inhibitor of the present invention uses self-synthesized fatty acid dihydrazide and fatty alcohol polyoxyethylene ether carboxylic acid as the main raw materials. The combined action of the two effectively solves the problems of thermal yellowing and phenol yellowing of fabrics, and at the same time does not have a negative impact on the original properties of the fabrics, such as strength, color fastness, and stability. Factors such as heat and light can cause oxidation reactions in fabrics, generating reactive substances such as free radicals. These reactive substances can trigger a series of chemical reactions, leading to the breakage and discoloration of the fabric molecular chains. Fatty acid dihydrazide can capture free radicals and terminate the oxidation reaction chain, thereby protecting the fabric from oxidative damage and preventing thermal yellowing and phenol yellowing. The molecular structure of fatty alcohol polyoxyethylene ether carboxylic acid contains both hydrophilic and hydrophobic groups, enabling it to precisely form a protective film on the fabric surface, especially on the surface of cotton fibers, effectively isolating the substances that cause thermal yellowing and phenol yellowing. At the same time, fatty alcohol polyoxyethylene ether carboxylic acid has an acid-base buffering capacity, which can maintain the stability of the system pH value and inhibit the oxidation of phenolic substances. Moreover, the surface activity of fatty alcohol polyoxyethylene ether carboxylic acid can evenly disperse phenolic substances and impurities, preventing them from reacting with the fibers, thus efficiently solving the problems of thermal yellowing and phenol yellowing of fabrics. In addition, fatty acid dihydrazide combines with the carboxylic acid group of fatty alcohol polyoxyethylene ether carboxylic acid through hydrogen bonds or ionic bonds to form a complex. This complex can, on the one hand, adsorb free radicals and terminate the oxidation reaction chain, and can also adsorb on the fabric surface to form a uniform protective layer. While jointly improving the resistance to thermal yellowing and phenol yellowing, it is beneficial to improve the washability and stability of the fabric.

[0008] To solve the above technical problems, a first aspect of the present invention provides a heat and phenol yellowing inhibitor, the raw material components of which by weight include: 10 - 20 parts of fatty acid dihydrazide, 5 - 10 parts of fatty alcohol polyoxyethylene ether carboxylic acid, 2 - 5 parts of surfactant, and 65 - 83 parts of deionized water.

[0009] In some embodiments of the present invention, the synthesis steps of the fatty acid dihydrazide include: dissolving the fatty acid in trans-dichloroethylene, successively adding hydrazine hydrate and p-toluenesulfonic acid, heating to 110 - 110 °C, and carrying out a reflux reaction; after cooling to 50 - 60 °C, pouring it into ice water to precipitate crystals, and obtaining the fatty acid dihydrazide through suction filtration, washing, and vacuum drying.

[0010] In some embodiments of the present invention, the fatty acid is selected from succinic acid or glutaric acid. When the fatty acid is succinic acid, the fatty acid dihydrazide is correspondingly succinic acid dihydrazide; when the fatty acid is glutaric acid, the fatty acid dihydrazide is correspondingly glutaric acid dihydrazide.

[0011] In some embodiments of the present invention, the molar ratio of the fatty acid to hydrazine hydrate is 1:(2.1 - 2.5).

[0012] In some embodiments of the present invention, when the fatty acid is glutaric acid, the molar ratio of glutaric acid to hydrazine hydrate is 1:(2.2 - 2.5).

[0013] In some embodiments of the present invention, when the fatty acid is succinic acid, the molar ratio of succinic acid to hydrazine hydrate is 1:(2.1 - 2.3).

[0014] In some embodiments of the present invention, the mass ratio of the fatty acid to trans-dichloroethylene is 1:(4 - 6).

[0015] In some embodiments of the present invention, the dosage of p-toluenesulfonic acid is 0.8 - 1.2 wt% of the fatty acid.

[0016] In some embodiments of the present invention, the time of the reflux reaction is 4 - 6 hours.

[0017] In some embodiments of the present invention, the washing is carried out with deionized water, and the mass ratio of the crystal to deionized water during washing is 1:(1.5 - 2.5).

[0018] In some embodiments of the present invention, the conditions for vacuum drying are drying for 3 - 6 hours under the conditions of 0.08 - 0.09 MPa and 50 - 70 °C.

[0019] In some embodiments of the present invention, the synthesis steps of the fatty alcohol polyoxyethylene ether carboxylic acid include: under an inert atmosphere, mixing a fatty alcohol with sodium hydroxide, heating to 120 - 130 °C, introducing ethylene oxide, and reacting to obtain a fatty alcohol polyoxyethylene ether; after cooling to 70 - 90 °C, first adding deionized water to dissolve, then adding chloroacetic acid, adjusting the pH value to 7 - 11, and stirring to obtain a crude product of fatty alcohol polyoxyethylene ether carboxylic acid; then adjusting the pH value to 6 - 8 and performing vacuum distillation to obtain the fatty alcohol polyoxyethylene ether carboxylic acid.

[0020] In some embodiments of the present invention, the fatty alcohol includes any one of isobutanol, isooctanol, and isomeric tridecanol. When the fatty alcohol is isobutanol, the fatty alcohol polyoxyethylene ether carboxylic acid is correspondingly isobutanol polyoxyethylene ether carboxylic acid; when the fatty alcohol is isooctanol, the fatty alcohol polyoxyethylene ether carboxylic acid is correspondingly isooctanol polyoxyethylene ether carboxylic acid; when the fatty alcohol is isomeric tridecanol, the fatty alcohol polyoxyethylene ether carboxylic acid is correspondingly isomeric tridecanol polyoxyethylene ether carboxylic acid.

[0021] In some embodiments of the present invention, the dosage of sodium hydroxide is 0.6 - 1.0% of the fatty alcohol.

[0022] In some embodiments of the present invention, when the fatty alcohol is isobutanol, the dosage of sodium hydroxide is 0.6 - 0.8% of isobutanol.

[0023] In some embodiments of the present invention, when the fatty alcohol is isooctanol, the amount of sodium hydroxide used is 0.7-0.9% of isooctanol.

[0024] In some embodiments of the present invention, when the fatty alcohol is isomeric tridecanol, the amount of sodium hydroxide used is 0.8-1.0% of isomeric tridecanol.

[0025] In some embodiments of the present invention, the molar ratio of the fatty alcohol to ethylene oxide is 1:(6-10).

[0026] In some embodiments of the present invention, when the fatty alcohol is isobutanol, the molar ratio of isobutanol to ethylene oxide is 1:(6-8).

[0027] In some embodiments of the present invention, when the fatty alcohol is isooctanol, the molar ratio of isooctanol to ethylene oxide is 1:(7-9).

[0028] In some embodiments of the present invention, when the fatty alcohol is isomeric tridecanol, the molar ratio of isomeric tridecanol to ethylene oxide is 1:(8-10).

[0029] In some embodiments of the present invention, the molar ratio of the fatty alcohol polyoxyethylene ether to deionized water is 1:(1.2-1.7).

[0030] In some embodiments of the present invention, when the fatty alcohol polyoxyethylene ether is isobutanol polyoxyethylene ether, the molar ratio of isobutanol polyoxyethylene ether to deionized water is 1:(1.2-1.5).

[0031] In some embodiments of the present invention, when the fatty alcohol polyoxyethylene ether is isooctanol polyoxyethylene ether, the molar ratio of isooctanol polyoxyethylene ether to deionized water is 1:(1.3-1.6).

[0032] In some embodiments of the present invention, when the fatty alcohol polyoxyethylene ether is isomeric tridecanol polyoxyethylene ether, the molar ratio of isomeric tridecanol polyoxyethylene ether to deionized water is 1:(1.4-1.7).

[0033] In some embodiments of the present invention, the molar ratio of the fatty alcohol polyoxyethylene ether to chloroacetic acid is 1:(1.1-1.3).

[0034] In some embodiments of the present invention, when the fatty alcohol polyoxyethylene ether is isobutanol polyoxyethylene ether, the molar ratio of isobutanol polyoxyethylene ether to chloroacetic acid is 1:(1.1-1.2).

[0035] In some embodiments of the present invention, when the fatty alcohol polyoxyethylene ether is isooctanol polyoxyethylene ether, the molar ratio of isooctanol polyoxyethylene ether to chloroacetic acid is 1:(1.15-1.25).

[0036] In some embodiments of the present invention, when the fatty alcohol polyoxyethylene ether is isomeric tridecyl alcohol polyoxyethylene ether, the molar ratio of isomeric tridecyl alcohol polyoxyethylene ether to chloroacetic acid is 1:(1.2 - 1.3).

[0037] In some embodiments of the present invention, the reaction conditions for introducing ethylene oxide are: reacting under a pressure of 0.2 - 0.4 MPa for 3 - 5 hours.

[0038] In some embodiments of the present invention, the conditions for vacuum distillation are: performing vacuum distillation for 1 - 3 hours under a vacuum degree of 0.08 - 0.09 MPa and a temperature of 60 - 80 °C.

[0039] In some embodiments of the present invention, the surfactant is a non - ionic surfactant, which is mainly used to improve the dispersibility and stability of each component.

[0040] In some embodiments of the present invention, the non - ionic surfactant is polyoxyethylene sorbitan fatty acid ester.

[0041] The second aspect of the present invention provides a preparation method of the above - mentioned heat - resistant and phenol - yellowing - resistant agent, comprising the following steps:

[0042] Mix the raw materials for preparing the heat - resistant and phenol - yellowing - resistant agent, raise the temperature, and carry out the reaction to obtain the heat - resistant and phenol - yellowing - resistant agent.

[0043] In some embodiments of the present invention, the preparation method of the heat - resistant and phenol - yellowing - resistant agent comprises the following steps:

[0044] Add fatty alcohol polyoxyethylene ether carboxylic acid to deionized water and stir for 15 - 20 minutes; then sequentially add fatty acid dihydrazide and surfactant, raise the temperature to 50 - 60 °C, and continue stirring for 1 - 2 hours; cool to room temperature to obtain the heat - resistant and phenol - yellowing - resistant agent.

[0045] The third aspect of the present invention provides a fabric, and the raw materials for preparing the fabric include the above - mentioned heat - resistant and phenol - yellowing - resistant agent.

[0046] In some embodiments of the present invention, the fabric is a cotton fabric or a nylon fabric.

[0047] The above - mentioned technical solutions of the present invention, compared with the prior art, have at least the following technical effects or advantages:

[0048] (1) The heat- and phenol-yellowing inhibitor of the present invention contains both self-synthesized fatty acid dihydrazide and fatty alcohol polyoxyethylene ether carboxylic acid. Among them: the fatty acid dihydrazide can capture free radicals and terminate the oxidation reaction chain, thereby protecting the fabric from oxidative damage and preventing heat yellowing and phenol yellowing; the molecular structure of the fatty alcohol polyoxyethylene ether carboxylic acid contains both hydrophilic and hydrophobic groups, enabling it to precisely form a protective film on the fabric surface, effectively isolating the substances that cause heat yellowing and phenol yellowing. At the same time, the fatty alcohol polyoxyethylene ether carboxylic acid has acid-base buffering ability, can maintain the stability of the system pH value, and inhibit the oxidation of phenolic substances. Moreover, the surface activity of the fatty alcohol polyoxyethylene ether carboxylic acid can evenly disperse phenolic substances and impurities, preventing them from reacting with the fibers, thus efficiently solving the problems of heat yellowing and phenol yellowing of the fabric. In addition, the fatty acid dihydrazide binds to the carboxylic acid group of the fatty alcohol polyoxyethylene ether carboxylic acid through hydrogen bonds or ionic bonds to form a complex. This complex not only improves heat- and phenol-yellowing resistance but also helps to improve the washability and stability of the fabric.

[0049] (2) The cotton fabric treated with the heat- and phenol-yellowing inhibitor of the present invention can achieve a heat yellowing resistance level of 4.9 - 5.0 and a phenol yellowing resistance level of 4.6 - 5.0, and has good strength, color fastness, and stability. Specific embodiments

[0050] The present invention will be specifically described below in conjunction with embodiments to facilitate the understanding of those skilled in the art. It is necessary to specifically point out here that the embodiments are only used to further illustrate the present invention and should not be construed as limiting the protection scope of the present invention. Those skilled in the art, based on the above-mentioned invention content, make non-essential improvements and adjustments to the present invention, which should still fall within the protection scope of the present invention. At the same time, for the raw materials not specifically described below, they are all commercially available products; for the process steps or preparation methods not specifically mentioned, they are all process steps or preparation methods known to those skilled in the art.

[0051] Example 1

[0052] A heat- and phenol-yellowing inhibitor, the raw material components of which are included by weight: 20 parts of glutaric acid dihydrazide, 8 parts of isobutanol polyoxyethylene ether carboxylic acid, 2 parts of polyoxyethylene sorbitan fatty acid ester, and 70 parts of deionized water.

[0053] The preparation method of the above heat- and phenol-yellowing inhibitor includes the following steps:

[0054] (1) Synthesis of glutaric dihydrazide: Clean and dry the reaction kettle equipped with a stirrer, thermometer, and reflux condenser; then add glutaric acid (purity ≥ 99%) to the reaction kettle, and then add trans-dichloroethylene as a solvent (the mass ratio of glutaric acid to trans-dichloroethylene is 1:5). Start stirring, and control the stirring speed at 200 r / min; slowly add hydrazine hydrate (the molar ratio of glutaric acid to hydrazine hydrate is 1:2.3), and then add p-toluenesulfonic acid (the dosage is 1 wt% of glutaric acid). Gradually heat up to 100 °C and reflux for 5 hours at this temperature. After the reaction is completed, cool the reaction solution to 55 °C, and then pour it into ice water, and white crystals will precipitate. Perform suction filtration, and wash the crystals 4 times with deionized water, and the amount of deionized water used for each washing is 2 times the mass of the crystals. Place the washed crystals in a vacuum drying oven and dry for 4 hours at 55 °C and a vacuum degree of 0.08 MPa to obtain glutaric dihydrazide with a purity ≥ 98%.

[0055] (2) Synthesis of isobutanol polyoxyethylene ether carboxylic acid: After carefully cleaning and drying the reaction kettle equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet device, add isobutanol (purity ≥ 99%), start stirring, accurately control the stirring speed at 200 r / min, and introduce nitrogen for 25 minutes to completely remove air. Add sodium hydroxide (the dosage is 0.7 wt% of isobutanol) as a catalyst and continue stirring for 20 minutes. Gradually heat up to 125 °C, and at this temperature, introduce ethylene oxide (purity ≥ 99.5%, the molar ratio of isobutanol to ethylene oxide is 1:7), and react for 4 hours under a reaction pressure of 0.3 MPa until ethylene oxide completely reacts to obtain isobutanol polyoxyethylene ether. Cool the etherification product to 75 °C, add deionized water (the dosage is 1.3 times the mass of isobutanol polyoxyethylene ether), stir to dissolve it completely. Add chloroacetic acid (the molar ratio of isobutanol polyoxyethylene ether to chloroacetic acid is 1:1.1), and at the same time slowly drip a 20% sodium hydroxide solution, accurately adjust the pH value of the reaction system between 9 and 10, and continue stirring and reacting for 4 hours to obtain a crude product of isobutanol polyoxyethylene ether carboxylic acid. Finally, adjust the pH value of the crude product of isobutanol polyoxyethylene ether carboxylic acid to 7.0 with a 15% hydrochloric acid solution, and then perform vacuum distillation for 2 hours at a vacuum degree of 0.08 MPa and a temperature of 65 °C to completely remove excess water and impurities to obtain isobutanol polyoxyethylene ether carboxylic acid with a purity ≥ 95%.

[0056] (3) Add 70 g of deionized water to the reaction kettle, start stirring at a speed of 220 r / min; slowly add 8 g of isobutanol polyoxyethylene ether carboxylic acid prepared in step (2), and stir for 16 minutes; then add 20 g of succinic dihydrazide prepared in step (1), and stir for 11 minutes; then add 2 g of polyoxyethylene sorbitan fatty acid ester, and stir for 11 minutes; heat up to 52 °C, stir and react for 1.2 hours, and cool to room temperature to obtain the heat-resistant and phenol-yellowing-resistant agent of this example.

[0057] Example 2

[0058] A heat-resistant and phenol-yellowing-resistant agent, the raw material components of which include, by weight: 18 parts of succinic dihydrazide, 5 parts of isooctanol polyoxyethylene ether carboxylic acid, 3 parts of polyoxyethylene sorbitan fatty acid ester, and 65 parts of deionized water.

[0059] The preparation method of the above heat-resistant and phenol-yellowing-resistant agent includes the following steps:

[0060] (1) Synthesis of succinic dihydrazide: Clean and dry the reaction kettle equipped with a stirrer, thermometer, and reflux condenser; then add succinic acid (purity ≥ 99%) to the reaction kettle, and then add trans-dichloroethylene as a solvent (the mass ratio of succinic acid to trans-dichloroethylene is 1:5), start stirring, and control the stirring speed at 200 r / min; slowly add hydrazine hydrate (the molar ratio of succinic acid to hydrazine hydrate is 1:2.2), and then add p-toluenesulfonic acid (the dosage is 1 wt% of succinic acid). Gradually heat up to 110 °C and reflux and react at this temperature for 4 hours. After the reaction is completed, cool the reaction solution to 55 °C, and then pour it into ice water, and white crystals will precipitate. Carry out suction filtration, and wash the crystals 4 times with deionized water, and the amount of deionized water used for each washing is 2 times the mass of the crystals. Place the washed crystals in a vacuum drying oven and dry them at 65 °C and a vacuum degree of 0.08 MPa for 5 hours to obtain succinic dihydrazide with a purity ≥ 97%.

[0061] (2) Synthesis of isooctyl alcohol polyoxyethylene ether carboxylic acid: After the reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet device is carefully cleaned and dried, isooctyl alcohol (purity ≥ 99%) is added, stirring is started, the stirring speed is accurately controlled at 180r / min, and nitrogen is introduced for 30 minutes to completely exclude the air. Sodium hydroxide (0.8wt% of isooctyl alcohol) is added as a catalyst and stirring is continued for 20 minutes. The temperature is gradually raised to 130°C, at which temperature, ethylene oxide (purity ≥ 99.5%, isooctyl alcohol to ethylene oxide molar ratio 1:8) is introduced, and the reaction is carried out at a reaction pressure of 0.3MPa for 5 hours until the ethylene oxide is completely reacted to obtain isooctyl alcohol polyoxyethylene ether. The etherification product is cooled to 80°C, deionized water (1.5 times the mass of isooctyl alcohol polyoxyethylene ether) is added, and stirred to fully dissolve it. Chloroacetic acid (isooctanol polyoxyethylene ether to chloroacetic acid molar ratio 1:1.2) was added, and at the same time, a 20% mass fraction sodium hydroxide solution was slowly added dropwise, and the pH value of the reaction system was accurately adjusted between 9.5 and 10.5, and the reaction was stirred continuously for 4 hours to obtain a crude isooctyl alcohol polyoxyethylene ether carboxylic acid. Finally, the pH value of the crude isooctyl alcohol polyoxyethylene ether carboxylic acid was adjusted to 7.5 with a 15% mass fraction hydrochloric acid solution, and then reduced pressure distillation was performed at a vacuum degree of 0.08 MPa and a temperature of 70°C for 2 hours to completely remove excess water and impurities, and isooctyl alcohol polyoxyethylene ether carboxylic acid with a purity of ≥95% was obtained.

[0062] (3) Add 65 g of deionized water to the reactor and start stirring at a speed of 250 r / min; slowly add 5 g of isooctyl polyoxyethylene ether carboxylic acid prepared in step (2) and stir for 18 minutes; then add 15 g of succinic acid dihydrazide prepared in step (1) and stir for 13 minutes; then add 3 g of polyoxyethylene sorbitan fatty acid ester and stir for 13 minutes; heat to 55° C., stir and react for 1.5 hours, and cool to room temperature to obtain the heat-resistant and anti-phenolic yellowing agent of this embodiment.

[0063] Example 3

[0064] A heat-resistant and phenol-resistant yellowing agent comprises the following raw material components by weight: 10 parts of glutaric acid dihydrazide, 10 parts of tridecyl isomerized alcohol polyoxyethylene ether carboxylic acid, 5 parts of polyoxyethylene sorbitan fatty acid ester, and 60 parts of deionized water.

[0065] The preparation method of the above-mentioned heat-resistant and anti-phenolic yellowing agent comprises the following steps:

[0066] (1) Synthesis of glutaric dihydrazide: Clean and dry the reaction kettle equipped with a stirrer, thermometer, and reflux condenser; then add glutaric acid (purity ≥ 99%) to the reaction kettle, and then add trans-dichloroethylene as a solvent (the mass ratio of glutaric acid to trans-dichloroethylene is 1:5). Start stirring, and control the stirring speed at 200 r / min; slowly add hydrazine hydrate (the molar ratio of glutaric acid to hydrazine hydrate is 1:2.3), and then add p-toluenesulfonic acid (the dosage is 1 wt% of glutaric acid). Gradually heat up to 100 °C and reflux for 5 hours at this temperature. After the reaction is completed, cool the reaction solution to 55 °C, and then pour it into ice water, and white crystals will precipitate. Carry out suction filtration, and wash the crystals 4 times with deionized water, and the amount of deionized water used for each washing is 2 times the mass of the crystals. Place the washed crystals in a vacuum drying oven and dry them for 4 hours at 55 °C and a vacuum degree of 0.08 MPa to obtain glutaric dihydrazide with a purity ≥ 98%.

[0067] (2) Synthesis of tridecyl isomeric alcohol polyoxyethylene ether carboxylic acid: After carefully cleaning and drying the reaction kettle equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet device, add tridecyl isomeric alcohol (purity ≥ 99%), start stirring, accurately control the stirring speed at 190 r / min, and introduce nitrogen for 35 minutes to completely remove air. Add sodium hydroxide (the dosage is 0.9 wt% of tridecyl isomeric alcohol) as a catalyst and continue stirring for 22 minutes. Gradually heat up to 135 °C, and at this temperature, introduce ethylene oxide (purity ≥ 99.5%, the molar ratio of tridecyl isomeric alcohol to ethylene oxide is 1:9), and react at a reaction pressure of 0.3 MPa for 6 hours until ethylene oxide completely reacts to obtain tridecyl isomeric alcohol polyoxyethylene ether. Cool the etherification product to 85 °C, add deionized water (the dosage is 1.6 times the mass of tridecyl isomeric alcohol polyoxyethylene ether), stir to dissolve it completely. Add chloroacetic acid (the molar ratio of tridecyl isomeric alcohol polyoxyethylene ether to chloroacetic acid is 1:1.2), and at the same time slowly drip a 20% sodium hydroxide solution, accurately adjust the pH value of the reaction system between 10 - 11, and continue stirring and reacting for 5 hours to obtain the crude product of tridecyl isomeric alcohol polyoxyethylene ether carboxylic acid. Finally, adjust the pH value of the crude product of tridecyl isomeric alcohol polyoxyethylene ether carboxylic acid to 7.5 with a 15% hydrochloric acid solution, and then carry out vacuum distillation for 2.5 hours at a vacuum degree of 0.08 MPa and a temperature of 75 °C to completely remove excess water and impurities to obtain tridecyl isomeric alcohol polyoxyethylene ether carboxylic acid with a purity ≥ 95%.

[0068] (3) Add 60 g of deionized water to the reaction kettle, start stirring at a speed of 280 r / min; slowly add 10 g of the tridecyl isomeric alcohol polyoxyethylene ether carboxylic acid prepared in step (2), and stir for 20 minutes; then add 10 g of the succinic dihydrazide prepared in step (1), and stir for 15 minutes; then add 5 g of polyoxyethylene sorbitan fatty acid ester, and stir for 15 minutes; heat up to 58 °C, stir and react for 1.8 hours, and cool to room temperature to obtain the heat and phenol yellowing resistant agent of this example.

[0069] Comparative Example 1

[0070] The difference between Comparative Example 1 and Example 3 is that the raw material components of the heat and phenol yellowing resistant agent in Comparative Example 1 do not contain tridecyl isomeric alcohol polyoxyethylene ether carboxylic acid, and its raw material components by weight include: 20 parts of succinic dihydrazide, 5 parts of polyoxyethylene sorbitan fatty acid ester, and 60 parts of deionized water.

[0071] Comparative Example 2

[0072] The difference between Comparative Example 2 and Example 3 is that the raw material components of the heat and phenol yellowing resistant agent in Comparative Example 2 do not contain succinic dihydrazide, and its raw material components by weight include: 20 parts of tridecyl isomeric alcohol polyoxyethylene ether carboxylic acid, 5 parts of polyoxyethylene sorbitan fatty acid ester, and 60 parts of deionized water.

[0073] Comparative Example 3

[0074] The difference between Comparative Example 3 and Example 3 is that in the raw material components of the heat and phenol yellowing resistant agent in Comparative Example 3, an equal amount of fatty alcohol polyoxyethylene ether carboxylate (AEC-10) is used to replace the tridecyl isomeric alcohol polyoxyethylene ether carboxylic acid in Example 3, and its raw material components by weight include: 10 parts of succinic dihydrazide, 10 parts of AEC-10, 5 parts of polyoxyethylene sorbitan fatty acid ester, and 60 parts of deionized water.

[0075] Comparative Example 4

[0076] The difference between Comparative Example 4 and Example 3 is that in the raw material components of the heat and phenol yellowing resistant agent in Comparative Example 4, an equal amount of oxalic dihydrazide is used to replace the succinic dihydrazide in Example 3, and its raw material components by weight include: 10 parts of oxalic dihydrazide, 10 parts of tridecyl isomeric alcohol polyoxyethylene ether carboxylic acid, 5 parts of polyoxyethylene sorbitan fatty acid ester, and 60 parts of deionized water.

[0077] Performance Test

[0078] 1. Heat Yellowing Resistance

[0079] According to the standard of AATCC 173-2019 "Evaluation of Heat Yellowing of Textiles", the heat yellowing resistance performance of the heat and phenol yellowing resistant agents prepared in Examples 1-3 and Comparative Examples 1-4 was tested respectively, and the results are shown in Table 1.

[0080] The specific test process is as follows: The heat and phenol yellowing resistant agent was formulated into a solution with a mass fraction of 5%. White fabrics of the same specification and material, including white cotton and white nylon, were divided into three groups. One group was used as the blank control group, and the other two groups were respectively soaked in the heat and phenol yellowing resistant agent solution for 30 minutes, and then taken out and dried in an oven at 60 °C. The treated fabrics and the blank control fabrics were simultaneously placed in a heat aging test chamber, with the temperature set at 120 °C and the relative humidity at 65%. The fabrics were taken out after 2 hours, 4 hours, 6 hours, and 8 hours respectively. The yellowing degree of the fabrics was rated using a standard gray scale, and the rating standard was from 1 to 5 levels. Level 1 indicates severe yellowing, and level 5 indicates no yellowing phenomenon.

[0081] 2. Phenol yellowing resistance

[0082] According to the standard of AATCC 163-2013 "Evaluation of Phenol Yellowing of Textiles", the phenol yellowing resistance performance of the heat and phenol yellowing resistant agents prepared in Examples 1-3 and Comparative Examples 1-4 was tested respectively, and the results are shown in Table 1.

[0083] The specific test process is as follows: The treated cotton fabric and the untreated cotton fabric (control group) were simultaneously placed in a closed environment containing phenolic compounds, with the temperature precisely controlled at 40 ± 2 °C and the relative humidity at 75 ± 5%. After being placed for 48 hours, they were taken out. The yellowing degree of the fabrics was rated using a standard gray scale, and the rating standard was from 1 to 5 levels. Level 1 indicates severe yellowing, and level 5 indicates no yellowing phenomenon.

[0084] Table 1:

[0085]

[0086] As can be seen from Table 1, the heat yellowing resistance level of the white fabrics treated with the heat and phenol yellowing resistant agents prepared in Examples 1-3 can reach 4.9-5.0 levels, and the phenol yellowing resistance level can reach 4.6-5.0 levels, simultaneously possessing excellent heat yellowing resistance and phenol yellowing resistance performance. Compared with Example 3, in Comparative Examples 1-4, due to the use of single dihydrazide glutarate and isomeric tridecyl alcohol polyoxyethylene ether carboxylic acid, or the use of an equal amount of sodium fatty alcohol polyoxyethylene ether carboxylate (AEC-10) to replace isomeric tridecyl alcohol polyoxyethylene ether carboxylic acid, and an equal amount of dihydrazide oxalate to replace dihydrazide glutarate, their heat yellowing resistance and phenol yellowing resistance performance both decreased to varying degrees, indicating that the raw material components of the heat and phenol yellowing resistant agent of the present invention have specificity, and there is a synergistic effect between dihydrazide glutarate and isomeric tridecyl alcohol polyoxyethylene ether carboxylic acid.

[0087] 3. Colorfastness

[0088] (1) Colorfastness to washing

[0089] According to the standard of GB / T 3921-2008 "Textiles - Tests for colour fastness - Colour fastness to soaping", the cotton fabrics treated with the heat and phenolic yellowing resistant agents prepared in Examples 1-3 and Comparative Examples 1-4 were respectively cut into specified sizes, put into a soap solution containing standard detergent, and washed for 30 minutes under the specified temperature of 40°C and mechanical stirring conditions. After washing, the fabrics were taken out, rinsed thoroughly with water, dried, and then the color change degree of the fabrics and the staining degree of the fabrics were rated using a grey scale. The rating standard is from 1 to 5 levels, with 5 levels indicating the best colorfastness and 1 level indicating the worst colorfastness. The test results are shown in Table 2.

[0090] (2) Colorfastness to rubbing

[0091] According to the standard of GB / T 3920-2008 "Textiles - Tests for colour fastness - Colour fastness to rubbing", a rubbing colorfastness tester was used to conduct dry rubbing and wet rubbing tests on the cotton fabrics treated with the heat and phenolic yellowing resistant agents prepared in Examples 1-3 and Comparative Examples 1-4 respectively. During dry rubbing, the dry rubbing cloth was fixed under the rubbing head, and the fabric was rubbed back and forth 10 times under the specified pressure. During wet rubbing, the rubbing cloth was first soaked, squeezed to the specified humidity, and then the same operation was carried out. After rubbing, the staining degree of the rubbing cloth was rated using a grey scale. The rating standard is from 1 to 5 levels, with 5 levels indicating the best colorfastness and 1 level indicating the worst colorfastness. The test results are shown in Table 2.

[0092] Table 2:

[0093]

[0094] As can be seen from Table 2, the colorfastness to washing and the colorfastness to rubbing of the white fabrics treated with the heat and phenolic yellowing resistant agents prepared in Examples 1-3 can reach 4-5 levels, which are equivalent to those of the fabrics in the untreated blank control group in terms of various colorfastness properties, indicating that the heat and phenolic yellowing resistant agent prepared by the present invention has no adverse effect on the colorfastness of the fabric. Compared with Example 3, the colorfastness to washing and the colorfastness to rubbing of Comparative Examples 1-4 have both decreased, indicating that the heat and phenolic yellowing resistant agent of the present invention has better washing resistance than the traditional heat and phenolic yellowing resistant agent.

[0095] 4. Tensile strength

[0096] According to the standard of GB / T 3923.1-2013 "Textiles - Tensile properties of fabrics - Part 1: Determination of maximum force and elongation at break (strip method)", the cotton fabrics treated with the heat- and phenol-yellowing-resistant agents prepared in Examples 1-3 and Comparative Examples 1-4 were respectively cut into long strips of specified size, and tensile tests were carried out on a universal material testing machine. The tensile speed was set at 100±10 mm / min, and the force value at the break of the fabric was recorded. Five parallel samples were tested for each example, and the average value was taken as the final result. The test results are shown in Table 3.

[0097] Table 3:

[0098]

[0099] As can be seen from Table 3, the average breaking strength of the cotton fabrics treated with the heat- and phenol-yellowing-resistant agents prepared in Examples 1-3 can reach 360-372 N, which is comparable to the average breaking strength of the untreated blank control group of cotton fabrics, indicating that the heat- and phenol-yellowing-resistant agent prepared in the present invention has no adverse effect on the strength of the fabric. Compared with Example 3, the average breaking strength of Comparative Examples 1-4 decreased, indicating that the heat- and phenol-yellowing-resistant agent of the present invention has better mechanical properties than the traditional heat- and phenol-yellowing-resistant agents.

[0100] 5. Stability

[0101] The heat- and phenol-yellowing-resistant agents prepared in Examples 1-3 were respectively filled into sealed containers and stored at different temperature conditions (including 4°C, 25°C, 40°C) for 3 months. Samples were taken out every 1 month to observe whether there were phenomena such as stratification, precipitation, and discoloration in their appearance, and to test whether there were obvious changes in indicators such as pH value and viscosity. The results showed that after being stored at different temperature conditions for 3 months, the appearance of the heat- and phenol-yellowing-resistant agents remained clear and transparent, without stratification, precipitation, and discoloration phenomena, and the change ranges of pH value and viscosity were both within ±5%, indicating that the heat- and phenol-yellowing-resistant agent prepared in the present invention has good storage stability.

[0102] For those of ordinary skill in the art to which the present invention pertains, several simple deductions or substitutions can be made without departing from the concept of the present invention, without the need for creative labor. Therefore, all simple improvements made by those skilled in the art based on the disclosure of the present invention should fall within the protection scope of the present invention. The above embodiments are the preferred embodiments of the present invention, and all processes similar to the present invention and equivalent changes made should belong to the protection scope of the present invention.

Claims

1. A heat-resistant and phenol yellowing inhibitor, characterized in that, Its raw material components by weight include: 10-20 parts of fatty acid dihydrazide, 5-10 parts of fatty alcohol polyoxyethylene ether carboxylic acid, 2-5 parts of surfactant, and 65-83 parts of deionized water.

2. The anti-thermal and anti-phenol yellowing agent according to claim 1, characterized in that The synthesis steps of the fatty acid dihydrazide include: dissolving the fatty acid in trans-dichloroethylene, successively adding hydrazine hydrate and p-toluenesulfonic acid, heating to 110-110 °C, and carrying out a reflux reaction; after cooling to 50-60 °C, pouring it into ice water to precipitate crystals, and obtaining the fatty acid dihydrazide through suction filtration, washing, and vacuum drying.

3. The anti-thermal and anti-phenol yellowing agent according to claim 2, wherein, The fatty acid is selected from succinic acid or glutaric acid.

4. The heat-resistant and phenol-yellowing-resistant agent according to claim 2 or 3, characterized in that, The molar ratio of the fatty acid to hydrazine hydrate is 1:(2.1-2.5); and / or, the mass ratio of the fatty acid to trans-dichloroethylene is 1:(4-6); and / or, the dosage of p-toluenesulfonic acid is 0.8-1.2 wt% of the fatty acid.

5. The anti-thermal and anti-phenol yellowing agent according to claim 1, wherein The synthesis steps of the fatty alcohol polyoxyethylene ether carboxylic acid include: under an inert atmosphere, mixing the fatty alcohol with sodium hydroxide, heating to 120-130 °C, introducing ethylene oxide, and carrying out a reaction to obtain fatty alcohol polyoxyethylene ether; after cooling to 70-90 °C, first adding deionized water to dissolve, then adding chloroacetic acid, adjusting the pH value to 7-11, and stirring to obtain a crude product of fatty alcohol polyoxyethylene ether carboxylic acid; then adjusting the pH value to 6-8 and carrying out vacuum distillation to obtain the fatty alcohol polyoxyethylene ether carboxylic acid.

6. The anti-thermal and anti-phenol yellowing agent according to claim 5, wherein The fatty alcohol is selected from any one of isobutanol, isooctanol, and isomeric tridecanol.

7. The anti-thermal and anti-phenol yellowing agent according to claim 5 or 6, characterized in that, The dosage of the sodium hydroxide is 0.6-1.0% of the fatty alcohol; and / or, the molar ratio of the fatty alcohol to ethylene oxide is 1:(6-10); and / or, the molar ratio of the fatty alcohol polyoxyethylene ether to deionized water is 1:(1.2-1.7); and / or, the molar ratio of the fatty alcohol polyoxyethylene ether to chloroacetic acid is 1:(1.1-1.3).

8. The anti-thermal and anti-phenol yellowing agent according to claim 1, wherein The surfactant is a non-ionic surfactant.

9. A preparation method of the heat-resistant and phenol-yellowing-resistant agent according to any one of claims 1-8, characterized in that, It includes the following steps: Mix the raw materials for preparing the heat-resistant and phenol-yellowing-resistant agent, heat up, and carry out a reaction to obtain the heat-resistant and phenol-yellowing-resistant agent.

10. A fabric, characterized in that, The raw materials for preparing the fabric include the heat-resistant and phenol-yellowing-resistant agent according to any one of claims 1-8.

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