Synthetic methods for polyalkyl polysaccharide compounds as substitutes for reactive printing urea

Abstract

This invention discloses a method for synthesizing a polyalkyl polysaccharide compound that is a substitute for reactive printing urea. The steps are as follows: (1) Acrylamide ethylenediamine, sodium 4-vinylbenzene methane sulfonate and pure water are thoroughly mixed and the pH of the solution is adjusted; (2) Initiator and solution from step (1) are added dropwise to a flask; (3) Polysaccharide is added to the flask, epichlorohydrin is added, an alkaline aqueous solution is added dropwise, and the pH is adjusted to neutral with acid; (4) The product from step (1) is placed in a flask, a nucleophilic reaction catalyst is added, and the aqueous solution from step (3) is added dropwise to obtain the target product, polyalkyl polysaccharide compound. This invention uses the above-mentioned method for synthesizing a polyalkyl polysaccharide compound that is a substitute for reactive printing urea. The synthesized polyalkyl polysaccharide compound can effectively improve the three functions of reactive dyes in sizing: water retention and moisture absorption, dispersion and compressibility, and fiber expansion. It can also effectively promote the color development of reactive dyes during evaporation and effectively reduce ammonia nitrogen emissions.

Description

Technical Field

[0001] This invention relates to the field of compound synthesis technology, and in particular to a method for synthesizing polyalkyl polysaccharide compounds as substitutes for reactive printing urea. Background Technology

[0002] Reactive dye printing is the most mainstream printing method for cotton and regenerated cellulose fiber fabrics. It boasts good pattern clarity and color fastness, and enjoys a very high market share in apparel fabrics, especially home textiles. The dyes and chemicals involved in reactive printing typically include thickeners, resist salts, reactive dyes, baking soda, and urea. Among these, urea has a nitrogen content (ammonia nitrogen content) as high as 46.7%, and its usage typically ranges from 5% to 20%, making it the primary source of excessive ammonia nitrogen emissions.

[0003] Currently, the wastewater discharge standards of printing and dyeing plants are usually between 50-80 ppm. Reducing ammonia nitrogen emissions usually requires paying high wastewater treatment costs. Therefore, replacing urea with high ammonia nitrogen emissions has become a new demand target for printing plants.

[0004] Urea is an essential auxiliary agent in the reactive dye printing process. Urea is a hygroscopic agent with a moisture absorption capacity of 24.4%. It is also a cosolvent used to prepare reactive dye pastes, helping to dissolve and stabilize the pastes. Its main functions for reactive dyes are as follows: (1) Although reactive dye molecules have hydrophilic sulfonic acid groups and hydroxyl groups, which already have good solubility, the amount of dye used during printing paste preparation is relatively high, and the water content is small, so the use of urea as a solubilizer is still necessary. (2) After reactive dye printing, after steam fixing, urea plays a hygroscopic role through amide bonds, promoting fiber swelling, which is beneficial to dye penetration and increasing the moisture absorption capacity of reactive dyes. It promotes the occurrence of affinity addition or substitution reactions, and the coloring effect of thermosetting reactive dyes is more significant. (3) As a water substitute in the paste. After high-temperature setting, some water in the paste will be lost, and urea will supplement some of the water and participate in the catalytic reaction of reactive dyes with cotton hydroxyl chemical bonds. Generally, the minimum amount of urea is 1%. When the amount of dye used exceeds 1%, the amount of urea used should be equal to that of the dye, or increased by another 2%-4%.

[0005] Developing urea alternatives for reactive printing is crucial for green production and energy conservation and emission reduction. Therefore, the development of such products is both necessary and urgent, and will contribute to the green development of the reactive printing industry. Summary of the Invention

[0006] The purpose of this invention is to provide a method for synthesizing polyalkyl polysaccharide compounds as a substitute for reactive printing urea. The synthesized polyalkyl polysaccharide compounds can effectively improve the three functions of reactive dyes in sizing: water retention and moisture absorption, dispersion and compatibilization, and fiber swelling. They can also effectively promote the color development of reactive dyes during steaming and effectively reduce ammonia nitrogen emissions.

[0007] To achieve the above objectives, this invention provides a method for synthesizing polyalkyl polysaccharide compounds as substitutes for reactive printing urea. The specific synthesis steps are as follows:

[0008] (1) Mix acryloyl ethylenediamine, sodium 4-vinylbenzene methane sulfonate and pure water thoroughly to form a homogeneous solution for later use. Adjust the pH of the solution to 7-7.5 using a pH adjuster.

[0009] (2) Take a small amount of the solution from step (1) and add the initiator to prepare the seed solution. Add the seed solution to a four-necked flask equipped with a thermometer, a constant pressure dropper, and a reflux condenser. Purge the air with nitrogen, turn on the stirring device, slowly heat to 65-98℃, keep warm for 5-10 minutes, and then slowly add the initiator and the solution prepared in step (1). Add the solution for 1-2 hours, keep warm for 2-4 hours after the addition is complete, and then release the material after the temperature drops below 50℃ for later use.

[0010] (3) Add the polysaccharide to a four-necked flask equipped with a thermometer, a constant pressure dropper, and a reflux condenser. Purge with nitrogen to remove air, turn on the stirring device, add epichlorohydrin, slowly heat to 110-130℃, slowly add an aqueous solution of alkali, and after the addition is complete, keep at 120-150℃ for 4-5 hours. Cool down to 70℃, add an appropriate amount of pure water and solvent, adjust the pH value to neutral with acid, and discharge the material for later use.

[0011] (4) In a four-necked flask equipped with a thermometer, a constant pressure dropper, and a reflux condenser, the product of step (1) is placed into the four-necked flask, the temperature is slowly raised to 110-130℃, a nucleophilic reaction catalyst is added, the mixture is stirred thoroughly, and the aqueous solution of the product of step (3) is slowly added dropwise over a period of 2 hours. After the addition is complete, the temperature is maintained for 3-5 hours before cooling and discharging to obtain the target product, polyalkyl polysaccharide compound.

[0012] Preferably, in step (2), the initiator is 0.05-0.15 parts, and the initiator is potassium persulfate or ammonium persulfate.

[0013] Preferably, in step (1), there are 20-30 parts of acryloyl ethylenediamine, 10-15 parts of sodium 4-vinylbenzene methane sulfonate, and 0.5-3 parts of pH adjuster, wherein the pH adjuster is 4-hydroxyethylpiperazine ethanesulfonic acid or 3-hydroxymethylaminomethane.

[0014] Preferably, in step (3), the polysaccharide is 15-25 parts, and the polysaccharide is sorbitol, xylitol, erythritol and mannitol.

[0015] Preferably, in step (3), 2-7 parts of alkali are used, and the alkali is sodium hydroxide or potassium hydroxide.

[0016] Preferably, in step (3), 1-5 parts of acid are used, and the acid is citric acid or acetic acid.

[0017] Preferably, in step (3), 5-15 parts of solvent are used, and the solvent is ethylene glycol monobutyl ether or diethylene glycol.

[0018] Preferably, in step (4), 0.5-5 parts of nucleophilic reaction catalyst are used, and the nucleophilic reaction catalyst is calcium acetate or zinc acetate.

[0019] Preferably, the chemical structural formula of the polyalkyl polysaccharide compound is as follows:

[0020]

[0021] The values ​​of m and n are both greater than 3.

[0022] The advantages and positive effects of the method for synthesizing the polyalkyl polysaccharide compound as a substitute for reactive printing urea according to the present invention are as follows:

[0023] 1. The polyalkyl polysaccharide compound synthesized in this invention can effectively absorb moisture and lock in water through the polyhydroxyl groups on the chain segments, providing favorable conditions for the reaction between dyes and the alcohol hydroxyl groups of cellulose. At the same time, the polyhydroxyl groups can also form hydrogen bonds with the hydroxyl groups of cellulose fibers, which can swell the fibers and facilitate the penetration of dyes.

[0024] 2. The sodium benzenesulfonate group of the alkyl backbone of this invention can effectively solubilize disperse dyes, resulting in more uniform color. It replaces urea and reduces ammonia nitrogen emissions by absorbing moisture to aid color development, swelling to aid penetration, and dispersing to aid dissolution, thus contributing to the green development of printing and dyeing enterprises.

[0025] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0026] Figure 1 This is a chemical structure diagram of the polyalkyl polysaccharide compound synthesized in this invention. Detailed Implementation

[0027] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments.

[0028] Unless otherwise defined, the technical or scientific terms used in this invention shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.

[0029] Example 1

[0030] In this embodiment, the components are added in parts by weight. The initiator is: potassium persulfate 0.1 parts; the polysaccharide is: sorbitol 20 parts, epichlorohydrin 10 parts; the alkali is: sodium hydroxide 3 parts; the pH adjuster is: 4-hydroxyethylpiperazine ethanesulfonic acid 1 part; the nucleophilic catalyst is: calcium acetate 1 part; the neutralizing acid is: citric acid 1 part; and the solvent is: ethylene glycol monobutyl ether 5 parts, acryloyl ethylenediamine 25 parts, and sodium 4-vinylbenzene methanesulfonate 15 parts.

[0031] The synthesis method of polyalkyl polysaccharide compounds as substitutes for reactive printing urea is as follows:

[0032] (1) Mix acryloyl ethylenediamine, sodium 4-vinylbenzene methane sulfonate and pure water thoroughly to form a homogeneous solution for later use. Adjust the pH of the solution to 7-7.5 using a pH adjuster.

[0033] (2) Take a small amount of the solution from step (1) and add the initiator to prepare the seed solution. Add the seed solution to a four-necked flask equipped with a thermometer, a constant pressure dropper, and a reflux condenser. Purge the air with nitrogen, turn on the stirring device, slowly heat to 65-98℃, keep warm for 5-10 minutes, and then slowly add the initiator and the solution prepared in step (1). Add the solution for 1-2 hours, keep warm for 2-4 hours after the addition is complete, and then release the material after the temperature drops below 50℃ for later use.

[0034] (3) Add the polysaccharide to a four-necked flask equipped with a thermometer, a constant pressure dropper, and a reflux condenser. Purge with nitrogen to remove air, turn on the stirring device, add epichlorohydrin, slowly heat to 110-130℃, slowly add an aqueous solution of alkali, and after the addition is complete, keep at 120-150℃ for 4-5 hours. Cool down to 70℃, add an appropriate amount of pure water and solvent, adjust the pH value to neutral with acid, and discharge the material for later use.

[0035] (4) In a four-necked flask equipped with a thermometer, a constant pressure dropper, and a reflux condenser, the product of step (1) is placed into the four-necked flask, the temperature is slowly raised to 110-130℃, a nucleophilic reaction catalyst is added, the mixture is stirred thoroughly, and the aqueous solution of the product of step (3) is slowly added dropwise over a period of 2 hours. After the addition is complete, the temperature is maintained for 3-5 hours before cooling and discharging to obtain the target product, polyalkyl polysaccharide compound.

[0036] Example 2

[0037] In this embodiment, the components are added in parts by weight. The initiator is: ammonium persulfate 0.1 parts; the polysaccharide is: xylitol 10 parts, erythritol 5 parts, epichlorohydrin 12 parts; the alkali is: potassium hydroxide 4 parts; the pH adjuster is: 3-hydroxymethylaminomethane 2 parts; the nucleophilic addition catalyst is: zinc acetate 1 part; the neutralizing acid is: acetic acid 2 parts; and the solvent is: pure water 15 parts, diethylene glycol 10 parts, acryloyl ethylenediamine 30 parts, and sodium 4-vinylbenzene methane sulfonate 10 parts.

[0038] The synthesis method of polyalkyl polysaccharide compounds as substitutes for reactive printing urea, and the specific synthesis steps are as follows:

[0039] (1) Mix acryloyl ethylenediamine, sodium 4-vinylbenzene methane sulfonate and pure water thoroughly to form a homogeneous solution for later use. Adjust the pH of the solution to 7-7.5 using a pH adjuster.

[0040] (2) Take a small amount of the solution from step (1) and add the initiator to prepare the seed solution. Add the seed solution to a four-necked flask equipped with a thermometer, a constant pressure dropper, and a reflux condenser. Purge the air with nitrogen, turn on the stirring device, slowly heat to 65-98℃, keep warm for 5-10 minutes, and then slowly add the initiator and the solution prepared in step (1). Add the solution for 1-2 hours, keep warm for 2-4 hours after the addition is complete, and then release the material after the temperature drops below 50℃ for later use.

[0041] (3) Add the polysaccharide to a four-necked flask equipped with a thermometer, a constant pressure dropper, and a reflux condenser. Purge with nitrogen to remove air, turn on the stirring device, add epichlorohydrin, slowly heat to 110-130℃, slowly add an aqueous solution of alkali, and after the addition is complete, keep at 120-150℃ for 4-5 hours. Cool down to 70℃, add an appropriate amount of pure water and solvent, adjust the pH value to neutral with acid, and discharge the material for later use.

[0042] (4) In a four-necked flask equipped with a thermometer, a constant pressure dropper, and a reflux condenser, the product of step (1) is placed into the four-necked flask, the temperature is slowly raised to 110-130℃, a nucleophilic reaction catalyst is added, the mixture is stirred thoroughly, and the aqueous solution of the product of step (3) is slowly added dropwise over a period of 2 hours. After the addition is complete, the temperature is maintained for 3-5 hours before cooling and discharging to obtain the target product, polyalkyl polysaccharide compound.

[0043] Comparative Example 1

[0044] A comparative experiment was conducted on the polyalkyl polysaccharide compound product synthesized in this invention, which is a urea substitute S, and urea. The experimental results are shown in Table 1.

[0045] The viscosity of the color paste was adjusted to 2000 mPa·s (4# / 6r) with 5% seaweed.

[0046] Table 1 Experimental Results

[0047] ① ② ③ ④ ⑤ ⑥ baking soda 3％ 3％ 3％ 3％ 3％ 3％ Anti-dyeing salt S 1％ 1％ 1％ 1％ 1％ 1％ Urea 15％ － 15％ － 10％ － Urea Replacement S － 3％ － 3％ － 2％ Active Brilliant Blue 5％ 5％ － － － － Active Turquoise － － 5％ 5％ － － Active Black － － － － 5％ 5％ K / S value 16.23 17.14 11.26 11.35 18.34 18.56

[0048] Table 1 shows the color yields (expressed as K / S values) of three different dyes with the addition of urea and with the addition of a urea substitute S, indicating that they can completely replace urea in the role of printing dyes.

[0049] Therefore, the present invention adopts the above-mentioned method for synthesizing polyalkyl polysaccharide compounds as substitutes for reactive printing urea. The synthesized polyalkyl polysaccharide compounds can effectively improve the three functions of reactive dyes in sizing: water retention and moisture absorption, dispersion and compatibilization, and fiber swelling. They can also effectively promote the color development of reactive dyes during steaming and effectively reduce ammonia nitrogen emissions.

[0050] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for synthesizing polyalkyl polysaccharide compounds as substitutes for reactive printing urea, characterized in that, The specific synthesis steps are as follows: (1) Mix acryloyl ethylenediamine, sodium 4-vinylbenzene methane sulfonate and pure water thoroughly to form a homogeneous solution for later use. Adjust the pH of the solution to 7-7.5 using a pH adjuster. (2) Take a small amount of the solution from step (1) and add the initiator to prepare the seed solution. Add the seed solution to a four-necked flask equipped with a thermometer, a constant pressure dropper, and a reflux condenser. Purge the air with nitrogen, turn on the stirring device, slowly heat to 65-98℃, keep warm for 5-10 minutes, and then slowly add the initiator and the solution prepared in step (1). Add the solution for 1-2 hours, keep warm for 2-4 hours after the addition is complete, and then release the material after the temperature drops below 50℃ for later use. (3) Add the polysaccharide to a four-necked flask equipped with a thermometer, a constant pressure dropper, and a reflux condenser. Purge with nitrogen to remove air, turn on the stirring device, add epichlorohydrin, and slowly heat to 110-130℃. Slowly add an aqueous solution of alkali. After the addition is complete, keep the temperature at 120-150℃ for 4-5 hours, then cool to 70℃. Add an appropriate amount of pure water and solvent, adjust the pH to neutral with acid, and set aside. The polysaccharide is 15-25 parts, and the polysaccharide is sorbitol, xylitol, erythritol, and mannitol. The alkali is 2-7 parts, and the alkali is sodium hydroxide and potassium hydroxide. The epichlorohydrin is 7-17 parts. (4) In a four-necked flask equipped with a thermometer, a constant pressure dropper, and a reflux condenser, the product of step (2) is placed into the four-necked flask, the temperature is slowly raised to 110-130℃, a nucleophilic reaction catalyst is added, the mixture is stirred thoroughly, and the aqueous solution of the product of step (3) is slowly added dropwise over a period of 2 hours. After the addition is complete, the temperature is maintained for 3-5 hours before cooling and discharging to obtain the target product, polyalkyl polysaccharide compound.

2. The method for synthesizing the polyalkyl polysaccharide compound as a substitute for reactive printing urea according to claim 1, characterized in that: In step (2), the initiator is 0.05-0.15 parts, and the initiator is potassium persulfate or ammonium persulfate.

3. The method for synthesizing the polyalkyl polysaccharide compound as a substitute for reactive printing urea according to claim 1, characterized in that: In step (1), 20-30 parts of acryloyl ethylenediamine, 10-15 parts of sodium 4-vinylbenzene methane sulfonate, and 0.5-3 parts of pH adjuster are used. The pH adjuster is 4-hydroxyethylpiperazine ethanesulfonic acid and 3-hydroxymethylaminomethane.

4. The method for synthesizing the polyalkyl polysaccharide compound as a substitute for reactive printing urea according to claim 1, characterized in that: In step (3), 1-5 parts of acid are used, and the acid is citric acid or acetic acid.

5. The method for synthesizing the polyalkyl polysaccharide compound as a substitute for reactive printing urea according to claim 1, characterized in that: In step (3), 5-15 parts of solvent are used, and the solvent is ethylene glycol monobutyl ether or diethylene glycol.

6. The method for synthesizing the polyalkyl polysaccharide compound as a substitute for reactive printing urea according to claim 1, characterized in that: In step (4), 0.5-5 parts of nucleophilic reaction catalyst are used, and the nucleophilic reaction catalyst is calcium acetate or zinc acetate.

7. The method for synthesizing the polyalkyl polysaccharide compound as a substitute for reactive printing urea according to claim 1, characterized in that: The chemical structural formula of the polyalkyl polysaccharide compound is as follows: The values ​​of m and n are both greater than 3, and the sugar alcohol segment is sorbitol.

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