阅读说明：本技术 一种纺织物整理用印染助剂及其制备方法 (Printing and dyeing auxiliary for textile fabric finishing and preparation method thereof ) 是由 不公告发明人 于 2021-08-17 设计创作，主要内容包括：本发明公开一种纺织物整理用印染助剂,包括如下重量份原料：多元醇单体30-45份、异氰酸酯单体20-28份、改性壳聚糖1-5份、催化剂0.3-0.5份和辅助单体2-7份；一种纺织物整理用印染助剂的制备方法,包括如下步骤：第一步、将多元醇单体真空度下脱水,调节预聚温度至70-80℃,加入经干燥的异氰酸酯单体、改性壳聚糖和催化剂,同时加入辅助单体,反应2-3h,得到预聚体；第二步、在温度为60-80℃的条件下,向预聚体加入甲乙酮肟,达到理论值时反应结束,反应结束后,将温度降为40℃,加入冰醋酸调节pH值,继续搅拌,然后加入去离子水,搅拌混合,得到一种纺织物整理用印染助剂。(The invention discloses a printing and dyeing auxiliary agent for textile fabric finishing, which comprises the following raw materials in parts by weight: 30-45 parts of polyol monomer, 20-28 parts of isocyanate monomer, 1-5 parts of modified chitosan, 0.3-0.5 part of catalyst and 2-7 parts of auxiliary monomer; a preparation method of a printing and dyeing auxiliary agent for textile finishing comprises the following steps: dehydrating a polyol monomer under vacuum degree, adjusting prepolymerization temperature to 70-80 ℃, adding a dried isocyanate monomer, modified chitosan and a catalyst, simultaneously adding an auxiliary monomer, and reacting for 2-3h to obtain a prepolymer; and secondly, adding methyl ethyl ketoxime into the prepolymer at the temperature of 60-80 ℃, finishing the reaction when the theoretical value is reached, reducing the temperature to 40 ℃ after the reaction is finished, adding glacial acetic acid to adjust the pH value, continuously stirring, then adding deionized water, and stirring and mixing to obtain the printing and dyeing auxiliary agent for textile finishing.)

1. The printing and dyeing auxiliary for textile finishing is characterized by comprising the following raw materials in parts by weight:

30-45 parts of polyol monomer, 20-28 parts of isocyanate monomer, 1-5 parts of modified chitosan, 0.3-0.5 part of catalyst and 2-7 parts of auxiliary monomer;

the printing and dyeing auxiliary for textile finishing is prepared by the following steps:

firstly, dehydrating a polyol monomer at 89-92 ℃ under the vacuum degree of 0.08-0.10MPa for 1-1.2h, adjusting the prepolymerization temperature to 70-80 ℃, adding an isocyanate monomer, modified chitosan and a catalyst, simultaneously adding an auxiliary monomer, and reacting for 2-3h to obtain a prepolymer;

and secondly, adding methyl ethyl ketoxime into the prepolymer at the temperature of 60-80 ℃, finishing the reaction when the theoretical value R =1.05-1.30 is reached, reducing the temperature to 40 ℃ after the reaction is finished, adding glacial acetic acid to adjust the pH value to 6-7, continuously stirring for 50-60min, then adding deionized water, and continuously stirring for 10-15min to obtain the printing and dyeing auxiliary agent for textile finishing.

2. The printing and dyeing assistant for textile finishing according to claim 1, wherein the polyol monomer is one or two of polyether polyol and polyester polyol mixed according to any proportion; the isocyanate monomer is one or more of isophorone diisocyanate, toluene diisocyanate and hexamethylene diisocyanate which are mixed according to any proportion; the catalyst is any one of triethylamine, diethylenetriamine and dimethylhexadecylamine; the R value in the second step is the NCO/OH molar ratio.

3. The printing and dyeing assistant for textile finishing according to claim 1, characterized in that the auxiliary monomer is prepared by the following steps:

and step S1, adding ethylene glycol diglycidyl ether into a reaction kettle, dropwise adding diethylamine under the conditions that the temperature is 55 ℃ and the rotating speed is 300r/min, controlling the diethylamine to be completely dropwise added within 50-60min, continuously reacting for 4-5h after the dropwise adding is finished, and removing redundant diethylamine under the conditions of 50 ℃ and-0.09 MPa after the reaction is finished to obtain the auxiliary monomer.

4. The printing and dyeing assistant for textile finishing according to claim 3, wherein the molar ratio of ethylene glycol diglycidyl ether to diethylamine in step S1 is 1: 2-2.2.

5. The printing and dyeing assistant for textile finishing according to claim 1, characterized in that the modified chitosan is prepared by the following steps:

step S21, adding chitosan into a reaction kettle, adding an acetic acid solution and a sodium acetate solution, adjusting the pH value to 5 by using a reagent, stirring for 10-20min at the temperature of 25 ℃ and the rotating speed of 300r/min, adding gamma-methacryloxypropyl trimethoxysilane and ammonium persulfate, raising the temperature to 60 ℃, keeping the rotating speed unchanged, carrying out reflux stirring reaction for 12h, after the reaction is finished, carrying out vacuum filtration on the obtained reaction liquid, washing a filter cake by using methanol, and after the washing is finished, drying to constant weight at the temperature of 30 ℃ to obtain a solid a;

step S22, adding epoxy chloropropane into a three-neck flask, setting the temperature to be 55 ℃ and the rotating speed to be 300r/min, dropwise adding triethylamine, keeping the temperature to be 50-54 ℃, stirring for reaction for 6 hours, standing for layering after the reaction is finished, keeping a lower layer solution, diluting with deionized water with the same volume, extracting with anhydrous ether, combining organic phases after extraction, transferring the obtained organic phase into a rotary evaporator, removing ether by rotary evaporation, and drying under the vacuum condition of 40 ℃ to constant weight to obtain an intermediate 1;

step S23, mixing the solid a with an acetic acid solution, adjusting the pH value to 9-10 by using a 1mol/L sodium hydroxide solution, stirring for 2h, centrifuging for 10min under the condition that the rotating speed is 3000r/min, reserving a lower-layer precipitate, washing the precipitate with distilled water until the washing liquid is neutral, and after washing is finished, mixing the washed precipitate and isopropanol according to a ratio of 1 g: 10-20mL of the mixture is mixed, the mixture is swelled at the temperature of 80 ℃ for 30-40min, then the intermediate 1 and deionized water are added, the temperature is kept unchanged, the mixture is stirred for 6h, after the stirring is finished, the obtained reaction solution is transferred to a rotary evaporator, isopropanol is removed through concentration under reduced pressure, the obtained reaction solution is mixed with 10 times of volume of ethanol-acetone mixed solution, a solid is separated out, a filter cake is obtained through suction filtration under reduced pressure, and the obtained filter cake is dried to constant weight at the temperature of 60 ℃ to obtain the modified chitosan.

6. The printing and dyeing assistant for textile finishing according to claim 5, wherein the concentration of the acetic acid solution in step S21 is 1mol/L, the concentration of the sodium acetate solution is 2mol/L, and the dosage ratio of the chitosan, the acetic acid solution and the sodium acetate solution is 2 g: 25mL of: 50 mL; the reagent used in the process of adjusting the pH is acetic acid solution or sodium acetate solution; in step S22, the molar ratio of the epoxy chloropropane to the triethylamine is 1.3: 1; in the step S23, the mass fraction of the acetic acid solution is 1%, and the ethanol-acetone mixed solution is prepared by mixing ethanol and acetone according to the volume ratio of 1: 1, mixing; the dosage ratio of the solid a, the acetic acid solution, the intermediate 1 and the deionized water is 1 g: 75mL of: 0.5-0.7 g: 25 mL.

7. The preparation method of the textile finishing printing and dyeing auxiliary agent as claimed in claim 1, characterized by comprising the following steps:

firstly, dehydrating a polyol monomer at 89-92 ℃ under the vacuum degree of 0.08-0.10MPa for 1-1.2h, adjusting the prepolymerization temperature to 70-80 ℃, adding a dried isocyanate monomer, modified chitosan and a catalyst, simultaneously adding an auxiliary monomer, and reacting for 2-3h to obtain a prepolymer;

and secondly, adding methyl ethyl ketoxime into the prepolymer at the temperature of 60-80 ℃, finishing the reaction when the theoretical value R =1.05-1.30 is reached, reducing the temperature to 40 ℃ after the reaction is finished, adding glacial acetic acid to adjust the pH value to 6-7, continuously stirring for 50-60min, then adding deionized water, and continuously stirring for 10-15min to obtain the printing and dyeing auxiliary agent for textile finishing.

Technical Field

The invention belongs to the technical field of textile printing and dyeing, and particularly relates to a printing and dyeing auxiliary for textile finishing and a preparation method thereof.

Background

With the increasing variety of fibers and the continuous development of dyeing technology, people have higher and higher requirements on textiles, which creates great challenges for improving the application performance of reactive dyes. The textile is required to have good light fastness, washing fastness, level dyeing property and dyeing reproducibility, and the dye uptake, lifting power and color fixing rate are required to be high during dyeing. The textile relates to a printing and dyeing treatment process in the preparation process, when the textile with poor dyeing fastness meets water, sweat, sun, saliva or physical friction, the dye is easy to fall off and fade, the appearance is affected, and fallen dye molecules or heavy metal ions can be absorbed by the human body through the skin to harm the health.

Cotton fiber (mainly composed of cellulose) is one of four natural fibers (cotton, wool, silk and hemp), and is more and more popular due to the characteristics of good hygroscopicity, heat retention, comfortableness and soft hand feeling, cleanness, health care, degradability, recycling and the like in the aspect of wearability. In order to meet the requirements of people for different colors of clothes fabrics, the fabrics are dyed. Both dyes and acid dyes are mainly fixed on fibers by Van der Waals force and hydrogen bonds, the fixing fastness is limited, and the dyes are easy to hydrolyze and fade in water, so that a color fixing agent is generally needed to improve the dyeing fastness of fabrics. The reactive dye contains reactive groups in the molecular structure, and can react with fibers to generate covalent bonds, so that the color fastness is relatively high.

Although a plurality of dyeing assistants exist in the prior art, the dyeing assistant has still unsatisfactory color enhancing and protecting performance, lacks or poor antibacterial performance, and the dyeing assistant in the existing market can not meet the requirements of people by far along with the improvement of the quality of life of the public.

Disclosure of Invention

The invention provides a printing and dyeing auxiliary for textile fabric finishing and a preparation method thereof.

The technical problems to be solved by the invention are as follows:

although a plurality of dyeing assistants exist in the prior art, the dyeing assistant has still unsatisfactory color enhancing and protecting performance, lacks or poor antibacterial performance, and the dyeing assistant in the existing market can not meet the requirements of people by far along with the improvement of the quality of life of the public.

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

the printing and dyeing auxiliary for textile finishing comprises the following raw materials in parts by weight:

30-45 parts of polyol monomer, 20-28 parts of isocyanate monomer, 1-5 parts of modified chitosan, 0.3-0.5 part of catalyst and 2-7 parts of auxiliary monomer;

the printing and dyeing auxiliary for textile finishing is prepared by the following steps:

firstly, dehydrating a polyol monomer at 89-92 ℃ under the vacuum degree of 0.08-0.10MPa for 1-1.2h, adjusting the prepolymerization temperature to 70-80 ℃, adding a dried isocyanate monomer, modified chitosan and a catalyst, simultaneously adding an auxiliary monomer, and reacting for 2-3h to obtain a prepolymer;

and secondly, adding methyl ethyl ketoxime into the prepolymer at the temperature of 60-80 ℃, finishing the reaction when the theoretical value R is 1.05-1.30, reducing the temperature to 40 ℃ after the reaction is finished, adding glacial acetic acid to adjust the pH value to 6-7, continuously stirring for 50-60min, then adding deionized water, and continuously stirring for 10-15min to obtain the printing and dyeing auxiliary agent for textile finishing.

Further, the polyol monomer is one or two of polyether polyol and polyester polyol which are mixed according to any proportion; the isocyanate monomer is one or more of isophorone diisocyanate, toluene diisocyanate and hexamethylene diisocyanate which are mixed according to any proportion; the catalyst is any one of triethylamine, diethylenetriamine and dimethylhexadecylamine; in the second step, the R value is the NCO/OH molar ratio, determined by infrared spectroscopy.

Further, the auxiliary monomer is prepared by the following steps:

and step S1, adding ethylene glycol diglycidyl ether into a reaction kettle, dropwise adding diethylamine under the conditions that the temperature is 55 ℃ and the rotating speed is 300r/min, controlling the diethylamine to be completely dropwise added within 50-60min, continuously reacting for 4-5h after the dropwise adding is finished, and removing redundant diethylamine under the conditions of 50 ℃ and-0.09 MPa after the reaction is finished to obtain the auxiliary monomer.

Further, the molar ratio of the ethylene glycol diglycidyl ether to the diethylamine in step S1 is 1: 2-2.2.

Further, the modified chitosan is prepared by the following steps:

step S21, adding chitosan into a reaction kettle, adding an acetic acid solution and a sodium acetate solution, adjusting the pH value to 5 by using a reagent, stirring for 10-20min at the temperature of 25 ℃ and the rotating speed of 300r/min, adding gamma-methacryloxypropyl trimethoxysilane and ammonium persulfate, raising the temperature to 60 ℃, keeping the rotating speed unchanged, carrying out reflux stirring reaction for 12h, after the reaction is finished, carrying out vacuum filtration on the obtained reaction liquid, washing a filter cake by using methanol, and after the washing is finished, drying to constant weight at the temperature of 30 ℃ to obtain a solid a; hydroxyl on the chitosan and double bonds on the gamma-methacryloxypropyltrimethoxysilane generate ether bonds, the gamma-methacryloxypropyltrimethoxysilane is introduced onto the chitosan, and a siloxane bond is introduced onto the chitosan to obtain a solid a.

Step S22, adding epoxy chloropropane into a three-neck flask, setting the temperature to be 55 ℃ and the rotating speed to be 300r/min, dropwise adding triethylamine, keeping the temperature to be 50-54 ℃, stirring for reaction for 6 hours, standing for layering after the reaction is finished, keeping a lower layer solution, diluting with deionized water with the same volume, extracting with anhydrous ether, combining organic phases after extraction, transferring the obtained organic phase into a rotary evaporator, removing ether by rotary evaporation, and drying under the vacuum condition of 40 ℃ to constant weight to obtain an intermediate 1;

step S23, mixing the solid a with an acetic acid solution, adjusting the pH value to 9-10 by using a 1mol/L sodium hydroxide solution, stirring for 2h, centrifuging for 10min under the condition that the rotating speed is 3000r/min, reserving a lower-layer precipitate, washing the precipitate with distilled water until the washing liquid is neutral, and after washing is finished, mixing the washed precipitate and isopropanol according to a ratio of 1 g: 10-20mL of the mixture is mixed, the mixture is swelled at the temperature of 80 ℃ for 30-40min, then the intermediate 1 and deionized water are added, the temperature is kept unchanged, the mixture is stirred for 6h, after the stirring is finished, the obtained reaction solution is transferred to a rotary evaporator, isopropanol is removed through concentration under reduced pressure, the obtained reaction solution is mixed with 10 times of volume of ethanol-acetone mixed solution, a solid is separated out, a filter cake is obtained through suction filtration under reduced pressure, and the obtained filter cake is dried to constant weight at the temperature of 60 ℃ to obtain the modified chitosan. And (2) reacting epichlorohydrin with triethylamine for substitution reaction to obtain a quaternary ammonium molecule intermediate 1, wherein the intermediate 1 contains an epoxy group with high reactivity, and the intermediate 1 reacts with an amino group on the solid a to carry out quaternization modification to obtain the modified chitosan.

Further, in the step S21, the concentration of the acetic acid solution is 1mol/L, the concentration of the sodium acetate solution is 2mol/L, and the usage ratio of the chitosan, the acetic acid solution and the sodium acetate solution is 2 g: 25mL of: 50 mL; the reagent used in the process of adjusting the pH is acetic acid solution or sodium acetate solution; in step S22, the molar ratio of the epoxy chloropropane to the triethylamine is 1.3: 1; in the step S23, the mass fraction of the acetic acid solution is 1%, and the ethanol-acetone mixed solution is prepared by mixing ethanol and acetone according to the volume ratio of 1: 1, mixing; the dosage ratio of the solid a, the acetic acid solution, the intermediate 1 and the deionized water is 1 g: 75mL of: 0.5-0.7 g: 25 mL.

A preparation method of a printing and dyeing auxiliary agent for textile finishing comprises the following steps:

firstly, dehydrating a polyol monomer at 89-92 ℃ under the vacuum degree of 0.08-0.10MPa for 1-1.2h, adjusting the prepolymerization temperature to 70-80 ℃, adding a dried isocyanate monomer, modified chitosan and a catalyst, simultaneously adding an auxiliary monomer, and reacting for 2-3h to obtain a prepolymer;

and secondly, adding methyl ethyl ketoxime into the prepolymer at the temperature of 60-80 ℃, finishing the reaction when the theoretical value R is 1.05-1.30, reducing the temperature to 40 ℃ after the reaction is finished, adding glacial acetic acid to adjust the pH value to 6-7, continuously stirring for 50-60min, then adding deionized water, and continuously stirring for 10-15min to obtain the printing and dyeing auxiliary agent for textile finishing.

The invention has the beneficial effects that:

firstly, preparing modified chitosan, wherein ether bonds are generated by hydroxyl on the chitosan and double bonds on gamma-methacryloxypropyltrimethoxysilane, the gamma-methacryloxypropyltrimethoxysilane is introduced onto the chitosan, a silicon oxygen bond is introduced onto the chitosan to obtain a solid a, epichlorohydrin and triethylamine are subjected to a reaction substitution reaction to prepare a quaternary ammonium molecular intermediate 1, the intermediate 1 contains an epoxy group with high reaction activity, and the intermediate 1 and amino groups on the solid a are subjected to a reaction to carry out quaternization modification to prepare the modified chitosan; and then carrying out prepolymerization reaction on a polyol monomer, an isocyanate monomer, the modified chitosan and an auxiliary monomer, and then carrying out end capping by methyl ethyl ketoxime to obtain the printing and dyeing auxiliary agent.

The chitosan is a natural cationic polysaccharide, has a structure similar to that of cellulose, and has good biocompatibility and degradability. The chitosan is applied to the fiber as a modifier, can cationize the fiber, improve the dyeing performance of the fiber, and endow the fiber with excellent characteristics of antibiosis, crease resistance and the like. According to the invention, the modified chitosan is introduced into the printing and dyeing auxiliary agent through the prepared modified chitosan. The silicon oxygen bond in the modified chitosan can be hydrolyzed with the surface of the fabric to form a crosslinking system, the softness and the smoothness of the surface of the fabric are improved, the quaternary ammonium salt cationic group in the modified chitosan has stronger polarity and can react with the anion of the dye to form insoluble dye salt precipitate, the dye is further fixed, and the fabric has better dyeing fastness. Has certain application prospect.

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.

Example 1

The printing and dyeing auxiliary for textile finishing comprises the following raw materials in parts by weight:

30 parts of polyol monomer, 20 parts of isocyanate monomer, 1 part of modified chitosan, 0.3 part of catalyst and 2 parts of auxiliary monomer;

the printing and dyeing auxiliary for textile finishing is prepared by the following steps:

firstly, dehydrating a polyol monomer at 89 ℃ under the vacuum degree of 0.08MPa for 1h, adjusting the prepolymerization temperature to 70 ℃, adding a dried isocyanate monomer, modified chitosan and a catalyst, simultaneously adding an auxiliary monomer, and reacting for 2h to obtain a prepolymer;

and secondly, adding methyl ethyl ketoxime into the prepolymer at the temperature of 60 ℃, finishing the reaction when the theoretical value R is 1.05, reducing the temperature to 40 ℃ after the reaction is finished, adding glacial acetic acid to adjust the pH value to 6, continuously stirring for 50min, then adding deionized water, and continuously stirring for 10min to obtain the printing and dyeing auxiliary agent for textile finishing.

Wherein the polyol monomer is polyether polyol; the isocyanate monomer is isophorone diisocyanate and toluene diisocyanate; the catalyst is triethylamine, and the R value in the second step is NCO/OH molar ratio and is determined by infrared spectroscopy.

Wherein the auxiliary monomer is prepared by the following steps:

and step S1, adding ethylene glycol diglycidyl ether into a reaction kettle, dropwise adding diethylamine under the conditions that the temperature is 55 ℃ and the rotating speed is 300r/min, controlling the diethylamine to be completely dropwise added within 50min, continuously reacting for 4h after the dropwise adding is finished, and removing redundant diethylamine under the conditions of 50 ℃ and-0.09 MPa after the reaction is finished to obtain the auxiliary monomer.

Wherein, in the step S1, the molar ratio of the ethylene glycol diglycidyl ether to the diethylamine is 1: 2.

the modified chitosan is prepared by the following steps:

step S21, adding chitosan into a reaction kettle, adding an acetic acid solution and a sodium acetate solution, adjusting the pH value to 5 by using a reagent, stirring for 10min at the temperature of 25 ℃ and the rotating speed of 300r/min, adding gamma-methacryloxypropyltrimethoxysilane and ammonium persulfate, raising the temperature to 60 ℃, keeping the rotating speed unchanged, carrying out reflux stirring reaction for 12h, after the reaction is finished, carrying out reduced pressure suction filtration on the obtained reaction liquid, washing a filter cake by using methanol, and after the washing is finished, drying to constant weight at the temperature of 30 ℃ to obtain a solid a;

step S22, adding epoxy chloropropane into a three-neck flask, setting the temperature to be 55 ℃ and the rotating speed to be 300r/min, dropwise adding triethylamine, keeping the temperature within 50 ℃, stirring for reaction for 6 hours, standing for layering after the reaction is finished, keeping a lower layer solution, diluting with deionized water with the same volume, extracting with anhydrous ether, combining organic phases after extraction, transferring the obtained organic phase into a rotary evaporator, removing ether by rotary evaporation, and drying under the vacuum condition of 40 ℃ to constant weight to obtain an intermediate 1;

step S23, mixing the solid a with an acetic acid solution, adjusting the pH value to 9 with 1mol/L sodium hydroxide solution, stirring for 2h, centrifuging for 10min at the rotating speed of 3000r/min, reserving the lower-layer precipitate, washing the precipitate with distilled water until the washing liquid is neutral, and after washing, mixing the washed precipitate with isopropanol according to a ratio of 1 g: 10mL of the mixture is mixed, the mixture is swelled at 80 ℃ for 30min, then the intermediate 1 and deionized water are added, the temperature is kept unchanged, the mixture is stirred for 6h, after the stirring is finished, the obtained reaction solution is transferred to a rotary evaporator, isopropanol is removed through decompression and concentration, the obtained reaction solution is mixed with 10 times of volume of ethanol-acetone mixed solution, solid is separated out, a filter cake is obtained through decompression and suction filtration, and the obtained filter cake is dried to constant weight at 60 ℃ to obtain the modified chitosan.

In the step S21, the concentration of the acetic acid solution is 1mol/L, the concentration of the sodium acetate solution is 2mol/L, and the dosage ratio of the chitosan, the acetic acid solution and the sodium acetate solution is 2 g: 25mL of: 50 mL; the reagent used in the process of adjusting the pH is acetic acid solution or sodium acetate solution; in step S22, the molar ratio of the epoxy chloropropane to the triethylamine is 1.3: 1; in the step S23, the mass fraction of the acetic acid solution is 1%, and the ethanol-acetone mixed solution is prepared by mixing ethanol and acetone according to the volume ratio of 1: 1, mixing; the dosage ratio of the solid a, the acetic acid solution, the intermediate 1 and the deionized water is 1 g: 75mL of: 0.5 g: 25 mL.

Example 2

The printing and dyeing auxiliary for textile finishing comprises the following raw materials in parts by weight:

38 parts of polyol monomer, 24 parts of isocyanate monomer, 3 parts of modified chitosan, 0.4 part of catalyst and 5 parts of auxiliary monomer;

the printing and dyeing auxiliary for textile finishing is prepared by the following steps:

firstly, dehydrating a polyol monomer at 90 ℃ under the vacuum degree of 0.08MPa for 1.1h, adjusting the prepolymerization temperature to 75 ℃, adding a dried isocyanate monomer, modified chitosan and a catalyst, simultaneously adding an auxiliary monomer, and reacting for 2.5h to obtain a prepolymer;

and secondly, adding methyl ethyl ketoxime into the prepolymer at the temperature of 70 ℃, finishing the reaction when the theoretical value R is 1.1, reducing the temperature to 40 ℃ after the reaction is finished, adding glacial acetic acid to adjust the pH value to 6, continuously stirring for 55min, then adding deionized water, and continuously stirring for 12min to obtain the printing and dyeing auxiliary agent for textile finishing.

Wherein the polyol monomer is polyester polyol; the isocyanate monomer is toluene diisocyanate; the catalyst is diethylenetriamine; in the second step, the R value is the NCO/OH molar ratio, determined by infrared spectroscopy.

Wherein the auxiliary monomer is prepared by the following steps:

and step S1, adding ethylene glycol diglycidyl ether into a reaction kettle, dropwise adding diethylamine under the conditions that the temperature is 55 ℃ and the rotating speed is 300r/min, controlling the diethylamine to be dropwise added within 55min, continuously reacting for 4.5h after dropwise adding is finished, and removing redundant diethylamine under the conditions of 50 ℃ and-0.09 MPa after the reaction is finished to obtain the auxiliary monomer.

Wherein, in the step S1, the molar ratio of the ethylene glycol diglycidyl ether to the diethylamine is 1: 2.1.

the modified chitosan is prepared by the following steps:

step S21, adding chitosan into a reaction kettle, adding an acetic acid solution and a sodium acetate solution, adjusting the pH value to 5 by using a reagent, stirring for 15min at the temperature of 25 ℃ and the rotating speed of 300r/min, adding gamma-methacryloxypropyltrimethoxysilane and ammonium persulfate, raising the temperature to 60 ℃, keeping the rotating speed unchanged, carrying out reflux stirring reaction for 12h, after the reaction is finished, carrying out reduced pressure suction filtration on the obtained reaction liquid, washing a filter cake by using methanol, and after the washing is finished, drying to constant weight at the temperature of 30 ℃ to obtain a solid a;

step S22, adding epoxy chloropropane into a three-neck flask, setting the temperature to be 55 ℃ and the rotating speed to be 300r/min, dropwise adding triethylamine, keeping the temperature within 52 ℃, stirring for reaction for 6 hours, standing for layering after the reaction is finished, keeping a lower layer solution, diluting with deionized water with the same volume, extracting with anhydrous ether, combining organic phases after extraction, transferring the obtained organic phase into a rotary evaporator, removing ether by rotary evaporation, and drying under the vacuum condition of 40 ℃ to constant weight to obtain an intermediate 1;

step S23, mixing the solid a with an acetic acid solution, adjusting the pH value to 9 with 1mol/L sodium hydroxide solution, stirring for 2h, centrifuging for 10min at the rotating speed of 3000r/min, reserving the lower-layer precipitate, washing the precipitate with distilled water until the washing liquid is neutral, and after washing, mixing the washed precipitate with isopropanol according to a ratio of 1 g: 15mL of the mixture is mixed, the mixture is swelled at the temperature of 80 ℃ for 35min, then the intermediate 1 and deionized water are added, the temperature is kept unchanged, the mixture is stirred for 6h, after the stirring is finished, the obtained reaction solution is transferred to a rotary evaporator, isopropanol is removed through decompression and concentration, the obtained reaction solution is mixed with 10 times of volume of ethanol-acetone mixed solution, solid is separated out, a filter cake is obtained through decompression and suction filtration, and the obtained filter cake is dried to constant weight at the temperature of 60 ℃ to obtain the modified chitosan.

In the step S21, the concentration of the acetic acid solution is 1mol/L, the concentration of the sodium acetate solution is 2mol/L, and the dosage ratio of the chitosan, the acetic acid solution and the sodium acetate solution is 2 g: 25mL of: 50 mL; the reagent used in the process of adjusting the pH is acetic acid solution or sodium acetate solution; in step S22, the molar ratio of the epoxy chloropropane to the triethylamine is 1.3: 1; in the step S23, the mass fraction of the acetic acid solution is 1%, and the ethanol-acetone mixed solution is prepared by mixing ethanol and acetone according to the volume ratio of 1: 1, mixing; the dosage ratio of the solid a, the acetic acid solution, the intermediate 1 and the deionized water is 1 g: 75mL of: 0.6 g: 25 mL.

Example 3

The printing and dyeing auxiliary for textile finishing comprises the following raw materials in parts by weight:

45 parts of polyol monomer, 28 parts of isocyanate monomer, 5 parts of modified chitosan, 0.5 part of catalyst and 7 parts of auxiliary monomer;

the printing and dyeing auxiliary for textile finishing is prepared by the following steps:

firstly, dehydrating a polyol monomer at 92 ℃ and under the vacuum degree of 0.10MPa for 1.2h, adjusting the prepolymerization temperature to 80 ℃, adding a dried isocyanate monomer, modified chitosan and a catalyst, simultaneously adding an auxiliary monomer, and reacting for 3h to obtain a prepolymer;

and secondly, adding methyl ethyl ketoxime into the prepolymer at the temperature of 80 ℃, finishing the reaction when the theoretical value R1.30 is reached, reducing the temperature to 40 ℃ after the reaction is finished, adding glacial acetic acid to adjust the pH value to 7, continuously stirring for 60min, then adding deionized water, and continuously stirring for 15min to obtain the printing and dyeing assistant for textile finishing.

Wherein the polyol monomer is polyether polyol; the isocyanate monomer is hexamethylene diisocyanate; the catalyst is dimethyl hexadecylamine; in the second step, the R value is the NCO/OH molar ratio, determined by infrared spectroscopy.

Wherein the auxiliary monomer is prepared by the following steps:

and step S1, adding ethylene glycol diglycidyl ether into a reaction kettle, dropwise adding diethylamine under the conditions that the temperature is 55 ℃ and the rotating speed is 300r/min, controlling the diethylamine to be completely dropwise added within 60min, continuously reacting for 5h after the dropwise adding is finished, and removing redundant diethylamine under the conditions of 50 ℃ and-0.09 MPa after the reaction is finished to obtain the auxiliary monomer.

Wherein, in the step S1, the molar ratio of the ethylene glycol diglycidyl ether to the diethylamine is 1: 2.2.

the modified chitosan is prepared by the following steps:

step S21, adding chitosan into a reaction kettle, adding an acetic acid solution and a sodium acetate solution, adjusting the pH value to 5 by using a reagent, stirring for 20min at the temperature of 25 ℃ and the rotating speed of 300r/min, adding gamma-methacryloxypropyltrimethoxysilane and ammonium persulfate, raising the temperature to 60 ℃, keeping the rotating speed unchanged, carrying out reflux stirring reaction for 12h, after the reaction is finished, carrying out reduced pressure suction filtration on the obtained reaction liquid, washing a filter cake by using methanol, and after the washing is finished, drying to constant weight at the temperature of 30 ℃ to obtain a solid a;

step S22, adding epoxy chloropropane into a three-neck flask, setting the temperature to be 55 ℃ and the rotating speed to be 300r/min, dropwise adding triethylamine, keeping the temperature within 54 ℃, stirring for reaction for 6 hours, standing for layering after the reaction is finished, keeping a lower layer solution, diluting with deionized water with the same volume, extracting with anhydrous ether, combining organic phases after extraction, transferring the obtained organic phase into a rotary evaporator, removing ether by rotary evaporation, and drying under the vacuum condition of 40 ℃ to constant weight to obtain an intermediate 1;

step S23, mixing the solid a with an acetic acid solution, adjusting the pH value to 10 by using a 1mol/L sodium hydroxide solution, stirring for 2h, centrifuging for 10min under the condition that the rotating speed is 3000r/min, reserving the lower-layer precipitate, washing the precipitate with distilled water until the washing liquid is neutral, and after washing is finished, mixing the washed precipitate with isopropanol according to a ratio of 1 g: 20mL of the mixture is mixed, the mixture is swelled at the temperature of 80 ℃ for 40min, then the intermediate 1 and deionized water are added, the temperature is kept unchanged, the mixture is stirred for 6h, after the stirring is finished, the obtained reaction solution is transferred to a rotary evaporator, isopropanol is removed through decompression and concentration, then the obtained reaction solution is mixed with 10 times of volume of ethanol-acetone mixed solution, solid is separated out, a filter cake is obtained through decompression and suction filtration, and the obtained filter cake is dried to constant weight at the temperature of 60 ℃ to obtain the modified chitosan.

In the step S21, the concentration of the acetic acid solution is 1mol/L, the concentration of the sodium acetate solution is 2mol/L, and the dosage ratio of the chitosan, the acetic acid solution and the sodium acetate solution is 2 g: 25mL of: 50 mL; the reagent used in the process of adjusting the pH is acetic acid solution or sodium acetate solution; in step S22, the molar ratio of the epoxy chloropropane to the triethylamine is 1.3: 1; in the step S23, the mass fraction of the acetic acid solution is 1%, and the ethanol-acetone mixed solution is prepared by mixing ethanol and acetone according to the volume ratio of 1: 1, mixing; the dosage ratio of the solid a, the acetic acid solution, the intermediate 1 and the deionized water is 1 g: 75mL of: 0.7 g: 25 mL.

Comparative example 1

The printing and dyeing auxiliary for textile finishing comprises the following raw materials in parts by weight:

30 parts of polyol monomer, 20 parts of isocyanate monomer, 1 part of modified chitosan, 0.3 part of catalyst and 2 parts of auxiliary monomer;

the printing and dyeing auxiliary for textile finishing is prepared by the following steps:

firstly, dehydrating a polyol monomer at 89 ℃ under the vacuum degree of 0.08MPa for 1h, adjusting the prepolymerization temperature to 70 ℃, adding a dried isocyanate monomer, modified chitosan and a catalyst, simultaneously adding an auxiliary monomer, and reacting for 2h to obtain a prepolymer;

and secondly, adding methyl ethyl ketoxime into the prepolymer at the temperature of 60 ℃, finishing the reaction when the theoretical value R is 1.05, reducing the temperature to 40 ℃ after the reaction is finished, adding glacial acetic acid to adjust the pH value to 6, continuously stirring for 50min, then adding deionized water, and continuously stirring for 10min to obtain the printing and dyeing auxiliary agent for textile finishing.

Wherein the polyol monomer is polyether polyol; the isocyanate monomer is isophorone diisocyanate and toluene diisocyanate; the catalyst is triethylamine, and the R value in the second step is NCO/OH molar ratio and is determined by infrared spectroscopy.

Wherein the auxiliary monomer is prepared by the following steps:

and step S1, adding ethylene glycol diglycidyl ether into a reaction kettle, dropwise adding diethylamine under the conditions that the temperature is 55 ℃ and the rotating speed is 300r/min, controlling the diethylamine to be completely dropwise added within 50min, continuously reacting for 4h after the dropwise adding is finished, and removing redundant diethylamine under the conditions of 50 ℃ and-0.09 MPa after the reaction is finished to obtain the auxiliary monomer.

Wherein, in the step S1, the molar ratio of the ethylene glycol diglycidyl ether to the diethylamine is 1: 2.

the modified chitosan is prepared by the following steps:

step S21, adding epoxy chloropropane into a three-neck flask, setting the temperature to be 55 ℃ and the rotating speed to be 300r/min, dropwise adding triethylamine, keeping the temperature within 50 ℃, stirring for reaction for 6 hours, standing for layering after the reaction is finished, keeping a lower layer solution, diluting with deionized water with the same volume, extracting with anhydrous ether, combining organic phases after extraction, transferring the obtained organic phase into a rotary evaporator, removing ether by rotary evaporation, and drying under the vacuum condition of 40 ℃ to constant weight to obtain an intermediate 1;

step S22, mixing chitosan and acetic acid solution, adjusting the pH value to 9 by using 1mol/L sodium hydroxide solution, stirring for 2h, centrifuging for 10min under the condition that the rotating speed is 3000r/min, reserving the lower-layer precipitate, washing the precipitate by using distilled water until the washing liquid is neutral, and after washing is finished, washing the washed precipitate and isopropanol according to the ratio of 1 g: 10mL of the mixture is mixed, the mixture is swelled at 80 ℃ for 30min, then the intermediate 1 and deionized water are added, the temperature is kept unchanged, the mixture is stirred for 6h, after the stirring is finished, the obtained reaction solution is transferred to a rotary evaporator, isopropanol is removed through decompression and concentration, the obtained reaction solution is mixed with 10 times of volume of ethanol-acetone mixed solution, solid is separated out, a filter cake is obtained through decompression and suction filtration, and the obtained filter cake is dried to constant weight at 60 ℃ to obtain the modified chitosan.

Wherein, the molar ratio of the epoxy chloropropane to the triethylamine in the step S21 is 1.3: 1; in the step S22, the mass fraction of the acetic acid solution is 1%, and the ethanol-acetone mixed solution is prepared by mixing ethanol and acetone according to the volume ratio of 1: 1, mixing; the dosage ratio of the chitosan, the acetic acid solution, the intermediate 1 and the deionized water is 1 g: 75mL of: 0.5 g: 25 mL.

Comparative example 2

The comparative example is a common printing and dyeing auxiliary agent for textile fabric finishing in the market.

The printing aids of examples 1-3 and comparative examples 1-2 were tested; dyeing fabric → padding printing and dyeing auxiliary agent (the padding allowance is 85%) → drying (130 ℃, 3 min). The rubbing fastness test method is determined according to the method of GB/T3920-2008 'color fastness to rubbing test of textiles'; the soaping fastness test method is determined according to the method of GB/T3921-2008 'color fastness to washing test for textiles';

the test results are shown in table 1 below:

TABLE 1

As can be seen from the above table 1, the printing and dyeing auxiliary prepared by the method has better fastness, better washing resistance, friction resistance and other performances, does not contain formaldehyde, is nontoxic and harmless, is safe and reliable, and does not pollute the environment. The silicon oxygen bond in the modified chitosan can be hydrolyzed with the surface of the fabric to form a crosslinking system, the softness and the smoothness of the surface of the fabric are improved, and the quaternary ammonium salt cation group in the modified chitosan has stronger polarity and can react with the anion of the dye to form insoluble dye salt precipitate to further fix the dye, so that the fabric has better color fastness.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.