CN102863813A - Synthesis and application of efficient composite type long-chain tertiary amine quatemary ammonium salt fluorescent whitening agents - Google Patents

Abstract

Synthesis and application of high-efficiency composite long-chain tertiary amine quaternary ammonium fluorescent whitening agent. The present invention relates to the synthesis and application of a series of compound fluorescent whitening agents containing dodecyl/tetradecyl, hexadecyl/octadecyl dimethyl tertiary ammonium salt DSD acid-triazine compound. Mainly used in papermaking, coatings, inks and textiles. The following synthesis steps are adopted: a. cyanuric chloride reacts with DSD acid at 0°C to synthesize a one-step condensation product; b. a mixture of one-step condensation product and dodecyl/tetradecyl or hexadecyl/octadecyl dimethyl tertiary amine Reaction to synthesize two-step condensation products; c. Two-step condensation products react with a series of amino compounds to synthesize a series of high-efficiency composite long-chain tertiary amine quaternary ammonium salt fluorescent whitening agents. The performance test and application results show that the synthetic whitening agent not only has low raw material price and high yield, but also has obvious whitening effect on cotton cloth under alkaline conditions, has very strong fluorescence emission performance, and has played a joint synergistic effect It is suitable for large-scale industrial production.

Description

Synthesis and application of high-efficiency composite long-chain tertiary amine quaternary ammonium salt fluorescent whitening agent

technical field

The invention relates to the technical field of fine chemicals, and provides the synthesis and application of a series of high-efficiency composite long-chain tertiary amine quaternary ammonium salt fluorescent whitening agents.

Background technique

Triazine-DSD acid fluorescent whitening agent, that is, triazine aminostilbene fluorescent whitening agent, is widely used in papermaking, textile, coating, detergent and other industries because of its high cost performance, and has become a research topic at home and abroad. And one of the most produced fluorescent whitening agents. Traditional triazine-DSD acid fluorescent whitening agents are mostly single-type fluorescent whitening agents, which not only have high raw material prices, weak fluorescence emission, but also poor whitening effect. Composite fluorescent whitening agents composed of two or more components are rarely reported. The two-component or multi-component fluorescent whitening agent does not interfere with the absorption and radiation of light, and the radiation wavelength range is widened, which enhances the apparent fluorescence intensity and produces a stronger whitening effect than a single component. Synergistic effect, this patent contains dodecyl/tetradecyl, hexadecyl/octadecyl dimethyl tertiary amine quaternary ammonium salt DSD acid-triazine high-efficiency composite long-chain tertiary amine quaternary ammonium salt fluorescence Whitening agent not only has low raw material price and high yield, but also has strong fluorescence emission performance. Through compound synergy, it has obvious whitening effect on filter paper and cotton cloth, and is suitable for large-scale industrial production and application. Therefore, the synthesis of dodecyl/tetradecyl, hexadecyl/octadecyl dimethyl tertiary ammonium quaternary ammonium DSD acid-triazine high-efficiency composite long-chain tertiary amine quaternary ammonium salt fluorescent whitening agent has important practical significance.

Prior to the present invention, technologies related to the present invention include: patent CN1287200A introduces a special liquid fluorescent whitening agent for the paper industry and its synthesis process. Its synthesis process includes four steps: raw material refining treatment, organic reaction synthesis, semi-finished product purification treatment, and refined and concentrated finished product. The raw materials are mainly ground to 500 mesh by vibrating sieve, and the semi-finished product purification treatment is to use the reverse osmosis device to purify the semi-finished product liquid, and the product is purified and stable in storage. Patent CN1303424A discloses a water-soluble complex of fluorescent whitening agent and quaternary ammonium compound substantially free of unwanted salts. Its complex is a complex reaction between sulfonated fluorescent whitening agent and specific quaternary ammonium complex, and then almost all the excess salt formed in the reaction process is removed to form a water-soluble complex. The purification techniques used are solvent extraction, phase separation, high pressure ultrafiltration and other filtration methods. Patent CN1411452A discloses a water-soluble amphoteric fluorescent whitening agent, which includes a free radical X that is characteristic of a whitening agent, X contains at least one anionic substituent, and at least one tertiary amino group Z is combined with at least one colorless , an essentially aliphatic polyquaternium-hydroxyl radical Y covalently bonded, Y comprising more than one quaternary ammonium group, each of which is optionally interrupted by one or more other heteroatoms and/or replace. Patent CN200510104309.6 discloses a quaternary ammonium salt fluorescent whitening agent. The synthesis method is that cyanuric chloride reacts with p-aminobenzenesulfonic acid, DSD acid and triethanolamine or triethylamine in turn to synthesize a quaternary ammonium salt-type triazinylaminostilbene fluorescent whitening agent.

At present, most triazine-DSD acid fluorescent whitening agents have disadvantages such as high raw material price, low yield, poor monotype performance, weak fluorescence emission, poor acid resistance, and low whiteness value.

Contents of the invention

In order to solve the shortcoming of above-mentioned background technology, the present invention proposes the synthesis and the application of high-efficiency compound type long-chain tertiary amine quaternary ammonium salt fluorescent whitening agent, it utilizes the composite type fluorescent whitening agent containing quaternary ammonium salt group to be an amphoteric compound, It has both the activity of optical fluorescent whitening agent and cationic auxiliary agent, which improves its strong acid resistance, combination with fiber and washing fastness, and greatly improves its practicability.

In order to solve the above problems, the present invention adopts the following technical solutions:

High-efficiency composite long-chain tertiary amine quaternary ammonium fluorescent whitening agent, its structure is as follows:

Wherein, _R is the compound group formed after the amino group on the amino compound loses a hydrogen atom, and the amino compound is respectively ethanol ammonia, diethanol ammonia, diethylamine, p-aminobenzoic acid, iminodiacetic acid, meta Any of chloroaniline, p-aminobenzenesulfonic acid, glutamic acid, L-tyrosine, leucine; R ₂ is -(CH ₂ ) ₁₅ CH ₃ , R ₃ is -(CH ₂ ) ₁₇ CH ₃ or R ₂ is -(CH ₂ ) ₁₁ CH ₃ , and R ₃ is -(CH ₂ ) ₁₃ CH ₃ .

The synthetic steps of above-mentioned composite long-chain tertiary amine quaternary ammonium salt optical brightener are as follows:

First, in a 1000mL three-neck flask, add 500mL deionized water and 0.1mol DSD acid (4,4`-diaminostilbene-disulfonic acid), ice bath, keep the temperature at 0~5°C, stir vigorously, batch by batch Add 0.2mol cyanuric chloride once, add dropwise 10% NaOH solution, keep the pH at 4, react for 3h; then add 0.2mol dodecyl/tetradecyl dimethyl tertiary amine or hexadecyl/octadecyl Dimethyl tertiary amine, adjust the pH to 8 with 10% NaOH solution, raise the temperature to 45°C, react for 4 hours, finally add 0.2mol of the above amino compound, adjust with 10% NaOH solution, keep the pH at 10, and raise the temperature to 90 ℃, reacted for 6 hours; after the reaction was completed, cooled to room temperature, transferred the liquid in the reactor to a large beaker, added 500mL deionized water, adjusted the pH to 3 with 10% hydrochloric acid solution, precipitated a solid, and obtained a high-efficiency composite type by suction filtration and drying Long-chain tertiary amine quaternary ammonium fluorescent whitening agent.

Application of high-efficiency composite long-chain tertiary amine quaternary ammonium salt fluorescent whitening agent to cotton cloth for fluorescent whitening.

The steps of the described application method are: carry out fluorescent whitening to the cotton cloth, in a beaker according to owf of 0%, 0.02%, 0.05%, 0.08%, 0.15%, 0.2%, 0.3%, liquor ratio 1:40, carry out In the dyeing bath, use 10% NaOH solution to adjust the pH to 11, dye the cotton cloth at room temperature for 30 minutes, take it out and dry it at room temperature or 60°C, and measure the whiteness performance.

The owf is the concentration of the dye bath, that is, the weight ratio of the whitening agent to the cotton cloth to be whitened, and the bath ratio is the ratio of the volume of the dye solution to the weight of the cotton cloth.

The invention synthesizes a series of long-chain tertiary amine quaternary ammonium salt type triazine-DSD acid composite fluorescent whitening agents. The composite whitening agents are not only cheap in raw material price, high in yield, but also have strong fluorescent emission performance. Due to the presence of cationic quaternary ammonium salt groups, this type of fluorescent whitening agent has the activity of a cationic auxiliary agent, and its dyeing rate and color fixation rate are better than non-quaternary ammonium salt fluorescent whitening agents. Fiber bonding and wash fastness. This whitening agent is a compound whitening agent. Through compounding and synergizing, it has obvious whitening effect on cotton cloth, and is suitable for large-scale industrial production and application.

Detailed ways

Example 1:

To a 1000mL three-neck flask equipped with a stirrer and a thermometer, add 500mL deionized water and 37.04g DSD acid in sequence. Adjust the pH to 4 and react for 3 hours; continue to raise the temperature of the reaction mixture to 45°C, add 48.29g of dodecyl/tetradecyldimethyl tertiary amine, adjust the pH to 8 with 10% NaOH solution, and react for 4 hours. Finally, add 26.62g of iminodiacetic acid, adjust the pH to 10 with 10% NaOH solution, raise the temperature to 90°C, react for 6h, cool to room temperature, transfer the liquid in the reactor to a large beaker, add 500mL of deionized water, and use 10 % hydrochloric acid solution to adjust the pH to 3, precipitated solid, filtered and dried to obtain the target compound.

Example 2:

To a 1000mL three-neck flask equipped with a stirrer and a thermometer, add 500mL deionized water and 37.04g DSD acid in sequence. Adjust the pH to 4 and react for 3 hours; continue to raise the temperature of the reaction mixture to 45°C, add 48.29g of dodecyl/tetradecyldimethyl tertiary amine, adjust the pH to 8 with 10% NaOH solution, and react for 4 hours. Finally, add 15.01g of glycine, adjust the pH to 10 with 10% NaOH solution, raise the temperature to 90°C, react for 6h, cool to room temperature, transfer the liquid in the reactor to a large beaker, add 500mL deionized water, and use 10% hydrochloric acid The pH of the solution was adjusted to 3, and a solid precipitated out, which was filtered and dried to obtain the target compound.

Example 3:

To a 1000mL three-neck flask equipped with a stirrer and a thermometer, add 500mL deionized water and 37.04g DSD acid in sequence. Adjust the pH to 4 and react for 3 hours; continue to raise the temperature of the reaction mixture to 45°C, add 48.29g of dodecyl/tetradecyldimethyl tertiary amine, adjust the pH to 8 with 10% NaOH solution, and react for 4 hours. Finally, add 26.24g of leucine, adjust the pH to 10 with 10% NaOH solution, raise the temperature to 90°C, react for 6h, cool to room temperature, transfer the liquid in the reactor to a large beaker, add 500mL of deionized water, and use 10% hydrochloric acid solution to adjust the pH to 3, precipitated solid, filtered and dried to obtain the target compound.

Example 4:

To a 1000mL three-neck flask equipped with a stirrer and a thermometer, add 500mL deionized water and 37.04g DSD acid in sequence. Adjust the pH to 4 and react for 3 hours; continue to raise the temperature of the reaction mixture to 45°C, add 59.51g of hexadecyl/octadecyldimethyl tertiary amine, adjust the pH to 8 with 10% NaOH solution, and react for 4 hours. Finally, add 12.22g of ethanol ammonia, adjust the pH to 10 with 10% NaOH solution, raise the temperature to 90°C, react for 6h, cool to room temperature, transfer the liquid in the reactor to a large beaker, add 500mL of deionized water, and use 10% hydrochloric acid solution to adjust the pH to 3, precipitated solid, filtered and dried to obtain the target compound.

Example 5:

To a 1000mL three-neck flask equipped with a stirrer and a thermometer, add 500mL deionized water and 37.04g DSD acid in sequence. Adjust the pH to 4 and react for 3 hours; continue to raise the temperature of the reaction mixture to 45°C, add 59.51g of hexadecyl/octadecyldimethyl tertiary amine, adjust the pH to 8 with 10% NaOH solution, and react for 4 hours. Finally, add 27.43g of p-aminobenzoic acid, adjust the pH to 10 with 10% NaOH solution, raise the temperature to 90°C, react for 6h, cool to room temperature, transfer the liquid in the reactor to a large beaker, add 500mL of deionized water, and use 10% hydrochloric acid solution adjusted the pH to 3, precipitated solid, filtered and dried to obtain the target compound.

Embodiment 6:

To a 1000mL three-neck flask equipped with a stirrer and a thermometer, add 500mL deionized water and 37.04g DSD acid in sequence. Adjust the pH to 4 and react for 3 hours; continue to raise the temperature of the reaction mixture to 45°C, add 59.51g of hexadecyl/octadecyldimethyl tertiary amine, adjust the pH to 8 with 10% NaOH solution, and react for 4 hours. Finally, add 21.51g m-chloroaniline, adjust the pH to 10 with 10% NaOH solution, raise the temperature to 90°C, react for 6h, cool to room temperature, transfer the liquid in the reactor to a large beaker, add 500mL deionized water, and use 10 % hydrochloric acid solution to adjust the pH to 3, precipitated solid, filtered and dried to obtain the target compound.

Embodiment 7:

Boil the cotton cloth in water for 30 minutes, take it out, rinse it with water, gently squeeze out the excess water, put the synthesized fluorescent whitening agent W1-W11 in a 200mL beaker according to the owf of 0%, 0.02%, 0.05%, 0.08%, 0.15%, 0.2%, 0.3% dyeing bath, bath ratio 1:40, adjust the pH to 11 with 10% NaOH solution, dye the treated cotton cloth according to the order of the number of dyeing vats, and keep turning, dye at room temperature for 30 minutes, wash with water Clean it, dry it in the air or dry it below 60°C, and measure the whiteness.

_R1 in W1-W11 are ethanolamine, diethanolamine, diethylamine, p-aminobenzoic acid, iminodiacetic acid, m-chloroaniline, p-aminobenzenesulfonic acid, glutamic acid, L-tyrosine, leuco The group formed after the amino group in amino acid loses a hydrogen atom, R ₂ is -(CH ₂ ) ₁₅ CH ₃ , R ₃ is -(CH ₂ ) ₁₇ CH ₃ , the whitening results are as described in Table 1:

Table 1 The whitening effect of high-efficiency composite long-chain tertiary amine quaternary ammonium salt fluorescent whitening agent on cotton cloth

In the table: owf is the dye bath concentration, FBs is the product number.

The results prove that the compound whitening agent is not only cheap in raw material price and high in yield, but also has strong fluorescence emission performance. Through compounding and synergizing, it has obvious whitening effect on cotton cloth, and is suitable for large-scale industrial production and application.

Claims (4)

1. efficient compound long chain tertiary amine quaternary ammonium salt white dyes, its structure is as follows:

Wherein, R ₁For the amino on the aminocompound loses a formed group of hydrogen atom, described aminocompound is respectively ethanol ammonia, diethanolamine, diethylamine, para-amino benzoic acid, iminodiethanoic acid, m-chloro aniline, Sulphanilic Acid, L-glutamic acid, TYR, any in the leucine; R ₂For-(CH ₂) ₁₅CH ₃, R ₃For-(CH ₂) ₁₇CH ₃Or R ₂For-(CH ₂) ₁₁CH ₃, R ₃For-(CH ₂) ₁₃CH ₃

2. such as the synthetic method of the described efficient compound long chain tertiary amine of claim l quaternary ammonium salt white dyes, it is characterized in that, step is as follows: at first in the 1000mL there-necked flask, add 500mL deionized water and 0.1mol DSD acid (4,4`-diaminobenzil-disulfonic acid), ice bath, temperature maintain 0 ~ 5 ℃, violent stirring, add in batches the 0.2mol cyanuric chloride, drip 10% NaOH solution, make pH be controlled at 4, reaction 3h; Then add 0.2mol 12/tetradecyl dimethyl tertiary amine or 16/octadecyl dimethyl tertiary amine, NaOH solution with 10% is regulated pH to 8, be warming up to 45 ℃, reaction 4h, add at last the above-mentioned aminocompound of 0.2mol, the NaOH solution with 10% is regulated, and makes pH remain on 10, be warming up to 90 ℃, reaction 6h; Be cooled to room temperature after reaction is finished, liquid rotating in the reactor is moved on in the large beaker, add the 500mL deionized water, the hydrochloric acid soln with 10% is regulated pH to 3, separates out solid, and the suction filtration drying obtains efficient compound long chain tertiary amine quaternary ammonium salt white dyes.

3. efficient compound long chain tertiary amine quaternary ammonium salt white dyes claimed in claim 1 carries out the application of fluorescent brightening to cotton.

4. cotton is carried out the application of fluorescent brightening aspect according to claims 3 described efficient compound long chain tertiary amine quaternary ammonium salt white dyess, it is characterized in that, cotton is boiled 30min in water, take out, the water flushing, extrude gently too much moisture, in beaker, be 0%, 0.02%, 0.05% with synthetic white dyes according to dye bath concentration owf, 0.08%, 0.15%, 0.2%, 0.3%; bath raio 1:40; carry out dye bath, regulate pH 11 with 10% NaOH solution, with the cotton 30min that dyes at ambient temperature; take out in room temperature or 60 ℃ lower dryly, survey the whiteness performance.