阅读说明：本技术 一种具有抗菌性能的涤纶染料的制备方法 (Preparation method of antibacterial polyester dye ) 是由 孙佩 于 2020-05-27 设计创作，主要内容包括：本发明公开了一种具有抗菌性能的涤纶染料的制备方法,具体制备过程如下：将分散颜料与巴豆酸酐反应得到不饱和分散颜料,将制备的不饱和分散颜料与邻羟基苯乙酮和甲基丙烯酸3-磺酸丙酯钾盐反应得到阴离子型分散颜料,然后将阴离子型分散颜料加入水中搅拌溶解,接着向其中加入硫代烷基氯,反应得到两性涤纶染料。本发明以分散染料为基体,在分散染料的分子链上同时引入阴离子和阳离子,使得染料具有两性,进而提高了染料的水溶性,使得染料通过水进行溶解,制备成水性染料,解决了现有的分散染料由于其水溶性较小,使用时通过有机物进行溶解使得制备的染色浆料中含有有机溶剂不仅对人体有害,并且印染废水排放后污染环境的问题。(The invention discloses a preparation method of a polyester dye with antibacterial property, which comprises the following specific preparation processes: reacting the dispersed pigment with crotonic anhydride to obtain unsaturated dispersed pigment, reacting the prepared unsaturated dispersed pigment with o-hydroxyacetophenone and 3-sulfopropyl methacrylate potassium salt to obtain anionic dispersed pigment, adding the anionic dispersed pigment into water, stirring and dissolving, adding thioalkyl chloride, and reacting to obtain the amphoteric polyester dye. According to the invention, the disperse dye is used as a matrix, and anions and cations are simultaneously introduced to the molecular chain of the disperse dye, so that the dye has amphipathy, the water solubility of the dye is further improved, the dye is dissolved through water to prepare the waterborne dye, and the problems that the existing disperse dye is small in water solubility, and the prepared dyeing slurry contains an organic solvent which is harmful to a human body and pollutes the environment after printing and dyeing wastewater is discharged when the existing disperse dye is dissolved through an organic matter during use are solved.)

1. A preparation method of polyester dye with antibacterial property is characterized by comprising the following specific preparation processes:

firstly, adding a dispersion pigment into an acetone solution, stirring and dissolving, then adding hydrochloric acid to adjust the pH value of the solution to 2, then adding crotonic anhydride into a reaction vessel, stirring and reacting for 7-8h at normal temperature, then evaporating the product to remove the solvent acetone therein, adding the product into water, heating to 100-;

secondly, simultaneously adding the unsaturated dispersion pigment and acetone prepared in the first step into a reaction kettle, stirring and dissolving, simultaneously adding sodium ethoxide and o-hydroxyacetophenone into the reaction kettle, stirring and mixing for 2-3min, heating to 90-100 ℃, performing reflux reaction for 5-6h, keeping the temperature unchanged, adding 3-propyl methacrylate potassium sulfonate, stirring and reacting for 3-4h, and then performing reduced pressure distillation to obtain the anionic dispersion pigment, wherein the reaction structural formula is shown as follows;

thirdly, adding the anionic dispersed pigment prepared in the second step into water, stirring and dissolving, then heating to 60-65 ℃, introducing nitrogen into a reaction container for 30min, then adding thioalkyl chloride, controlling the temperature to be constant, carrying out reflux reaction for 3-4h, then carrying out evaporation concentration and then carrying out reduced pressure distillation to obtain the amphoteric polyester dye, wherein the reaction structural formula is shown as follows;

2. the method for preparing polyester dye with antibacterial property as claimed in claim 1, wherein 9-10mL of acetone solution is added to per gram of dispersed pigment, and 0.23-0.25g of crotonic anhydride is added.

3. The method for preparing polyester dye with antibacterial property as claimed in claim 1, wherein 0.53-0.58g of sodium ethoxide, 0.16-0.17g of o-hydroxyacetophenone and 0.22-0.24g of 3-propyl acrylate potassium sulfonate are added to each gram of unsaturated dispersion pigment.

4. The method for preparing polyester dye with antibacterial property as claimed in claim 1, wherein 0.18-0.2g of thioalkyl chloride is added to each gram of anionic dispersion pigment.

5. The preparation method of the polyester dye with antibacterial property according to claim 1, wherein the specific preparation process of the thioalkyl chloride is as follows:

step 1: dissolving thiourea in water, adding the solution into a reaction kettle, stirring the solution for 30-40min in an ice-water bath, adding epoxy chloropropane into the reaction kettle, stirring the solution in the ice-water bath for reaction for 2-3h, heating the reaction product to normal temperature, stirring the reaction product for reaction for 3-4h, separating the liquid of the obtained product, drying the obtained organic phase, and distilling the organic phase to obtain an episulfide compound;

step 2: adding the episulfide compound prepared in the step 1 into a reaction kettle, then adding hydrochloric acid solution with the concentration of 2mol/L into the reaction kettle, stirring the mixture at normal temperature for reaction for 1 to 2 hours, and then carrying out reduced pressure distillation to obtain the thioalkyl chloride.

6. The preparation method of polyester dye with antibacterial property according to claim 5, wherein the ratio of thiourea and epichlorohydrin is 1: mixing at a ratio of 0.82-0.84.

7. The method for preparing polyester dye with antibacterial property according to claim 5, wherein 6-7mL of hydrochloric acid solution with concentration of 2mol/L is added into each gram of episulfide compound.

Technical Field

The invention belongs to the field of dye preparation, and relates to a preparation method of a polyester dye with antibacterial property.

Background

The disperse dye has small molecules and contains no water-soluble group structurally, and can be uniformly dispersed in the dyeing solution by virtue of the action of the dispersant to carry out dyeing. The dye can dye polyester fiber, acetate fiber and polyamide fiber to become special dye for terylene, but because the water solubility is small, the prepared dye slurry contains organic solvent which is harmful to human body when being dissolved by organic matter during use, and pollutes the environment after the printing and dyeing wastewater is discharged, and meanwhile, the existing terylene is composed of short aliphatic hydrocarbon chain, ester group, benzene ring and terminal alcoholic hydroxyl group. Except that two terminal alcoholic hydroxyl groups exist in the terylene, the terylene does not have other polar groups, so that the terylene is easy to generate static electricity after friction to adsorb dust, and the terylene causes the dirt of the fabric.

Disclosure of Invention

The invention aims to provide a preparation method of a polyester dye with antibacterial property, which takes a disperse dye as a matrix, and simultaneously introduces anions and cations on the molecular chain of the disperse dye, so that the dye has amphipathy, and further the water solubility of the dye is improved, so that the dye is directly dissolved by water during dyeing to prepare the waterborne dye, and the problems that the existing disperse dye has small water solubility, and the prepared dyeing slurry contains an organic solvent which is harmful to a human body and pollutes the environment after printing and dyeing wastewater is discharged during use are solved.

The purpose of the invention can be realized by the following technical scheme:

a preparation method of polyester dye with antibacterial property comprises the following specific preparation processes:

firstly, adding a dispersed pigment into an acetone solution, stirring and dissolving, then adding hydrochloric acid to adjust the pH value of the solution to 2, then adding crotonic anhydride into a reaction vessel, stirring and reacting for 7-8h at normal temperature, then evaporating the product to remove the solvent acetone therein, adding water, heating to 100-110 ℃, stirring and mixing for 10-12min, and filtering while hot to obtain a solid product, namely the unsaturated dispersed pigment, wherein the reaction structural formula is as follows, 9-10mL of the acetone solution is added into each gram of the dispersed pigment, and 0.23-0.25g of the crotonic anhydride is added, and the dispersed pigment contains a large amount of amino groups, so that acylation reaction can be carried out with the crotonic anhydride under an acidic condition, and then a crotonic acid group is introduced onto the dispersed pigment;

secondly, adding the unsaturated dispersion pigment and acetone prepared in the first step into a reaction kettle at the same time, stirring and dissolving, adding sodium ethoxide and o-hydroxyacetophenone into the reaction kettle, stirring and mixing for 2-3min, heating to 90-100 ℃, carrying out reflux reaction for 5-6h, then adding 3-propyl methacrylate potassium salt while keeping the temperature unchanged, stirring and reacting for 3-4h, and then carrying out reduced pressure distillation to obtain the anionic dispersion pigment, wherein 0.53-0.58g of sodium ethoxide is added into each gram of the unsaturated dispersion pigment, 0.16-0.17g of o-hydroxyacetophenone is added, 0.22-0.24g of 3-propyl acrylate potassium salt is added, the reaction structural formula is shown in the specification, potassium sulfonate groups are introduced into the dispersion pigment to improve the water solubility of the pigment, and static electricity generated by rubbing cloth after dyeing is positive charge, the resin can perform electrical neutralization reaction with anionic groups contained in the pigment, so that static electricity is eliminated, and the polyester fabric is prevented from adsorbing dust due to static electricity generated by friction, so that the fabric is easily polluted;

thirdly, adding the anion type dispersion pigment prepared in the second step into water, stirring and dissolving, then heating to 60-65 ℃, introducing nitrogen into a reaction container for 30min, then adding thioalkyl chloride into the anion type dispersion pigment, controlling the temperature to be constant, carrying out reflux reaction for 3-4h, then carrying out reduced pressure distillation after evaporation concentration to obtain the amphoteric polyester dye, wherein the reaction structural formula is shown as follows, 0.18-0.2g of thioalkyl chloride is added into each gram of anion type dispersion pigment, quaternary ammonium group is introduced into the polyester dye, the antibacterial performance can be effectively realized, meanwhile, hydrogen contained in the pigment and introduced phenolic hydroxyl can be dropped off to react with free radicals to lose activity, further the free radical reaction is inhibited, but hydroperoxide generated by the reaction is decomposed into new free radicals under certain concentration, and the oxidation reaction of the free radicals is promoted, meanwhile, the sulfur element in the thiol group can convert hydroperoxide into a stable non-free radical compound, so that the oxidation of a polymer material is completely inhibited, a stabilizing effect is achieved, the ultraviolet aging can be effectively prevented, the prepared polyester dye has high antibacterial and ultraviolet-proof performance, and the introduction of the quaternary ammonium group improves the water solubility of the pigment;

the preparation process of the thioalkyl chloride is as follows:

step 1: dissolving thiourea in water, adding the solution into a reaction kettle, stirring the solution for 30-40min in an ice-water bath, adding epoxy chloropropane into the reaction kettle, stirring the solution in the ice-water bath for reaction for 2-3h, heating the reaction product to normal temperature, stirring the reaction product for reaction for 3-4h, separating the liquid of the obtained product, drying the obtained organic phase, and distilling the organic phase to obtain an episulfide compound; wherein the thiourea and the epichlorohydrin are mixed according to the mass ratio of 1: mixing at a ratio of 0.82-0.84;

step 2: adding the episulfide compound prepared in the step 1 into a reaction kettle, adding a hydrochloric acid solution with the concentration of 2mol/L into the reaction kettle, stirring the mixture at normal temperature for reaction for 1 to 2 hours, and then carrying out reduced pressure distillation to obtain thioalkyl chloride, wherein 6 to 7mL of the hydrochloric acid solution with the concentration of 2mol/L is added into each gram of the episulfide compound; because the episulfide compound contains the episulfide group, the ring-opening reaction can be carried out under the acidic condition, and alkyl chloride and thiol group are introduced into the product.

The invention has the beneficial effects that:

1. according to the invention, the disperse dye is used as a matrix, and anions and cations are simultaneously introduced to the molecular chain of the disperse dye, so that the dye has amphipathy, and further the water solubility of the dye is improved, and the dye is directly dissolved by water during dyeing to prepare the waterborne dye, thereby solving the problems that the existing disperse dye has small water solubility, and the prepared dyeing slurry contains an organic solvent which is harmful to a human body and pollutes the environment after printing and dyeing wastewater is discharged during use due to the dissolution of organic matters.

2. According to the invention, phenolic hydroxyl and a large number of quaternary ammonium salt groups are introduced into the dye, the phenolic hydroxyl has certain antibacterial property, and meanwhile, the antibacterial property of the fabric can be improved by the large number of quaternary ammonium salt groups introduced into the dye.

3. According to the invention, the potassium sulfonate group is introduced into the dispersed pigment, so that the water solubility of the pigment can be improved, and meanwhile, after dyeing, static electricity generated by rubbing of the cloth is positive charge and can be subjected to an electric neutralization reaction with an anionic group contained in the pigment, so that the static electricity is eliminated, and the problem that the polyester fabric is easy to stain due to the fact that the static electricity generated by rubbing adsorbs dust is solved.

4. The dyes prepared by the invention all contain phenolic hydroxyl and sulfur elements, hydrogen in the phenolic hydroxyl can drop and react with free radicals to make the free radicals lose activity so as to inhibit the free radical reaction, but hydroperoxide generated by the reaction is decomposed into new free radicals at a certain concentration and promotes the oxidation reaction of the free radicals, meanwhile, the sulfur element in the thiol group can convert the hydroperoxide into stable non-free radical compounds so as to completely inhibit the oxidation of polymer materials, play a role in stabilization and further effectively prevent the ultraviolet aging effect, so that the prepared polyester dye has high aging resistance, can resist aging and has no change in color when irradiated by high-intensity ultraviolet rays for a long time, and further effectively solves the problem that the disperse dye is an organic dye which contains unsaturated groups and is easy to age and discolor under the action of the ultraviolet rays, further causing the color change of the dyed terylene and influencing the beauty.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.