阅读说明：本技术 一种不吸附甲醛的锦纶抗热黄变剂及其制备方法 (Polyamide anti-thermal yellowing agent not adsorbing formaldehyde and preparation method thereof ) 是由 彭远森 汤永华 于 2019-09-07 设计创作，主要内容包括：本发明公开了一种不吸附甲醛的锦纶抗热黄变剂及其制备方法,其中,所述锦纶抗热黄变剂由以下组分组成：含氮杂环结构的抗氧化剂20-70％；去离子水20-78％；氢氧化钠NaOH 2-10％。其制备方法为：使用500ml的四口烧瓶,将溶于溶剂中的含氮杂环结构的抗氧化剂按总质量的20-70％加入至烧瓶中,加入20-78％的去离子水调节成5-40％的有效含量,搅拌20分钟,加入2-10％的氢氧化钠NaOH调至溶液PH值＝5.0-7.0,得到澄清液体状产品,即为不吸附甲醛的锦纶抗热黄变剂的成品。本发明的锦纶抗热黄变剂不吸附甲醛,抗热黄变效果良好,水溶性优异,且工艺简单、可操作性强、不产生污染物,成本低廉,对人类健康友好,具有广阔的市场前景。(The invention discloses a nylon anti-thermal yellowing agent not adsorbing formaldehyde and a preparation method thereof, wherein the nylon anti-thermal yellowing agent comprises the following components: 20-70% of antioxidant containing nitrogen heterocyclic ring structure; 20-78% of deionized water; 2-10% of sodium hydroxide NaOH. The preparation method comprises the following steps: adding an antioxidant with a nitrogen heterocyclic ring structure dissolved in a solvent into a 500ml four-neck flask according to 20-70% of the total mass, adding 20-78% of deionized water to adjust the effective content to 5-40%, stirring for 20 minutes, adding 2-10% of sodium hydroxide (NaOH) to adjust the pH value of the solution to 5.0-7.0, and obtaining a clear liquid product, namely the finished product of the nylon anti-thermal yellowing agent which does not adsorb formaldehyde. The nylon anti-thermal yellowing agent disclosed by the invention does not adsorb formaldehyde, has a good anti-thermal yellowing effect, is excellent in water solubility, simple in process, strong in operability, free of pollutant generation, low in cost, friendly to human health and wide in market prospect.)

1. The nylon anti-thermal yellowing agent which does not adsorb formaldehyde is characterized in that: the composite material comprises the following components in percentage by mass: 20-70% of antioxidant (containing solvent) with nitrogen heterocyclic structure; 20-78% of deionized water; 2-10% of sodium hydroxide NaOH.

2. The nylon anti-thermal yellowing agent not adsorbing formaldehyde according to claim 1, characterized in that: the nylon anti-thermal yellowing agent not adsorbing formaldehyde comprises the following components in percentage by mass: 30-60% of antioxidant (containing solvent) with nitrogen heterocyclic structure; 30-68% of deionized water; 3-9% of sodium hydroxide NaOH.

3. The nylon anti-thermal yellowing agent not adsorbing formaldehyde according to claim 1, characterized in that: the nylon anti-thermal yellowing agent not adsorbing formaldehyde comprises the following components in percentage by mass: 50% of an antioxidant (containing a solvent) containing a nitrogen heterocyclic structure; 47% of deionized water; 3 percent of sodium hydroxide NaOH.

4. A preparation method of a nylon anti-thermal yellowing agent not adsorbing formaldehyde comprises the following steps:

(1) Synthesis of antioxidant containing nitrogen heterocyclic structure: adding 9-69.9% of solvent into a 500ml four-neck flask according to the mass ratio, starting stirring, adding 10-30% of hydrazine at the speed of 2 drops/second, heating to 80 ℃ after the dropwise addition is finished, adding 20-60% of medium-short chain aliphatic diacid 5 times, adding 0.1-1.0% of catalyst after the addition is finished, controlling the temperature of the materials to be 90-130 ℃, keeping the temperature, stirring for 2-5 hours, and cooling to room temperature to obtain the antioxidant containing the nitrogen heterocyclic ring structure and dissolved in the solvent;

(2) Compounding: adding the synthesized antioxidant containing the nitrogen heterocyclic ring structure dissolved in the solvent into a 500ml four-neck flask according to 20-70% of the total mass, adding 20-78% of deionized water to adjust the effective content to 5-40%, stirring for 20 minutes, adding 2-10% of sodium hydroxide (NaOH) to adjust the pH value of the solution to 5.0-7.0, and obtaining a clear liquid product, namely the finished product of the nylon anti-thermal yellowing agent which does not adsorb formaldehyde.

5. The preparation method of the chinlon anti-thermal yellowing agent not adsorbing formaldehyde as claimed in claim 4, wherein the preparation method comprises the following steps: in the step (1): the solvent is organic acid or organic alcohol ether, such as formic acid, methanol, acetic acid, ethanol, oxalic acid, malonic acid, or succinic acid.

6. The method for preparing the nylon anti-thermal yellowing agent not adsorbing formaldehyde according to claim 4, wherein in the step (1): the hydrazine is one of hydrazine hydrate or unsym-dimethylhydrazine.

7. The method for preparing the nylon anti-thermal yellowing agent not adsorbing formaldehyde according to claim 4, wherein in the step (1): the short-chain aliphatic diacid is one of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.

8. the method for preparing the nylon anti-thermal yellowing agent not adsorbing formaldehyde according to claim 4, wherein in the step (1): the catalyst is one of sulfuric acid, potassium bisulfate and sodium bisulfate.

Technical Field

The invention relates to a printing and dyeing auxiliary agent, in particular to a nylon anti-thermal yellowing agent not adsorbing formaldehyde and a preparation method thereof.

background

The polyamide is also called polyamide fiber or nylon, and has a plurality of amide groups in the molecular structure. Spandex, also known as polyurethane fiber, has many urethane groups in its molecular structure. Due to the existence of amide groups and amino groups, the nylon/polyurethane elastic fabric has the defects of easy yellowing, brittleness and the like under the action of light and heat. Especially in the high-temperature processing process, such as heat setting, especially in the high-temperature pre-setting and underwear fabric compression molding, yellowing and color change are easy to occur, even the fiber is brittle and the strength is reduced to cause aging phenomenon, the appearance quality of the product is influenced, and meanwhile, the physical and mechanical properties of chinlon and spandex are seriously influenced, so the wearability of the chinlon and spandex is greatly reduced, and therefore, the anti-thermal yellowing finishing is a very important link in the dyeing and finishing processing process. The addition of the thermal yellowing resistant agent can prevent the chinlon and blended fabric thereof, especially the chinlon/ammonia elastic fabric from being oxidized and damaged at high temperature in the dyeing and finishing process, and improve the yellowing, color and luster and performance change caused by the action of heat, light, moisture and nitrogen oxide.

There are currently a number of anti-thermal yellowing products on the market for nylon/spandex stretch finishing, but these products are essentially ADH-containing products. ADH is adipic acid dihydrazide for short in English, and the structural formula is as follows: structural formula (xvi): h₂NHNCO(CH₂)4CONHNH₂The CAS is: 1071-93-8. ADH is a bifunctional compound with a symmetrical structure, is mainly used in the industries of paint auxiliary agents, metal deactivators, water treatment agents, printing ink, adhesives and the like, takes adipic acid, methanol and hydrazine hydrate as raw materials for reaction, and is prepared into [6-7 ] through multi-step crystallization, drying and purification]. However, ADH has more active chemical property and can generate acyl with aldehydeThe chemical reaction, which is also used as a formaldehyde scavenger, has the following reaction mechanism:

In the above reaction, the terminal amine group of ADH and formaldehyde form a hydrazone linkage of C ═ N structure. Because of this reversible reaction, formaldehyde is released again under certain conditions. After the brocade/ammonia elastic fabric is provided with the anti-thermal yellowing agent product containing the ADH, the ADH in the fabric can adsorb formaldehyde in a storage environment, and particularly, when finished clothes and clothes finished by the non-ironing resin containing free formaldehyde are mixed or displayed in a new decoration shop, the condition that the formaldehyde content exceeds the standard is easy to occur in the later detection of the clothes. Formaldehyde has strong stimulation to the protoplasm of biological cells, causes respiratory inflammation and dermatitis, is determined as carcinogenic and teratogenic by the world health organization, and the free formaldehyde content of textile products is strictly controlled by the regulations or standards of various countries.

The invention patent of patent publication No. CN103012216A 'HN-130 anti-yellowing agent synthesis process' proposes synthesizing 1, 6-hexamethylene-bis (N, N-dimethyl semicarbazide) as a polyamide and spandex fiber anti-yellowing agent, and has the problems of high cost and poor water solubility; patent publication No.: the invention patent CN105133313B 'an anti-yellowing agent for nylon' proposes that carbohydrazide is used as a polyamide and spandex fiber anti-yellowing agent, and the problem of adsorbing formaldehyde similar to ADH also exists.

Therefore, the research and development of a nylon anti-thermal yellowing agent which does not adsorb formaldehyde, has good anti-thermal yellowing effect, excellent water solubility, simple process, strong operability and low cost, and a synthetic method and an application process thereof become problems to be solved by technical personnel in the field.

Disclosure of Invention

the invention provides a nylon anti-thermal yellowing agent which does not adsorb formaldehyde and a preparation method thereof in order to solve the defects in the prior art.

The above object of the present invention is achieved by the following technical means: the nylon anti-thermal yellowing agent capable of not adsorbing formaldehyde comprises the following components in percentage by mass: 20-70% of antioxidant (containing solvent) with nitrogen heterocyclic structure; 20-78% of deionized water; 2-10% of sodium hydroxide NaOH.

Preferably, the nylon anti-thermal yellowing agent not adsorbing formaldehyde comprises the following components in percentage by mass: 30-60% of antioxidant (containing solvent) with nitrogen heterocyclic structure; 30-68% of deionized water; 3-9% of sodium hydroxide NaOH.

Preferably, the nylon anti-thermal yellowing agent not adsorbing formaldehyde comprises the following components in percentage by mass: 50% of an antioxidant (containing a solvent) containing a nitrogen heterocyclic structure; 47% of deionized water; 3 percent of sodium hydroxide NaOH.

A preparation method of a nylon anti-thermal yellowing agent not adsorbing formaldehyde comprises the following steps:

(1) Synthesis of antioxidant containing nitrogen heterocyclic structure: adding 9-69.9% of solvent into a 500ml four-neck flask according to the mass ratio, starting stirring, adding 10-30% of hydrazine at the speed of 2 drops/second, heating to 80 ℃ after the dropwise addition is finished, adding 20-60% of medium-short chain aliphatic diacid 5 times, adding 0.1-1.0% of catalyst after the addition is finished, controlling the temperature of the materials to be 90-130 ℃, keeping the temperature, stirring for 2-5 hours, and cooling to room temperature to obtain the antioxidant containing the nitrogen heterocyclic ring structure and dissolved in the solvent;

(2) compounding: adding the synthesized antioxidant containing the nitrogen heterocyclic ring structure dissolved in the solvent into a 500ml four-neck flask according to 20-70% of the total mass, adding 20-78% of deionized water to adjust the effective content to 5-40%, stirring for 20 minutes, adding 2-10% of sodium hydroxide (NaOH) to adjust the pH value of the solution to 5.0-7.0, and obtaining a clear liquid product, namely the finished product of the nylon anti-thermal yellowing agent which does not adsorb formaldehyde.

Further, in step (1): the solvent is organic acid or organic alcohol ether, such as formic acid, methanol, acetic acid, ethanol, oxalic acid, malonic acid, or succinic acid.

Further, in step (1): the hydrazine is one of hydrazine hydrate or unsym-dimethylhydrazine.

Further, in step (1): the short-chain aliphatic diacid is one of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.

Further, in step (1): the catalyst is one of sulfuric acid, potassium bisulfate and sodium bisulfate.

Compared with the prior art, the invention has the advantages that: the nylon anti-thermal yellowing agent disclosed by the invention does not adsorb formaldehyde, has a good anti-thermal yellowing effect, is excellent in water solubility, simple in process, strong in operability, free of pollutant generation, low in cost, friendly to human health and wide in market prospect.

Detailed Description

The present invention will be described in more detail with reference to examples.