WO2020232863A1

WO2020232863A1 - Method for preparing antibacterial and anti-wrinkle hydrogel and use thereof in textiles

Info

Publication number: WO2020232863A1
Application number: PCT/CN2019/102264
Authority: WO
Inventors: 余晨
Original assignee: Yu Chen
Priority date: 2019-05-23
Filing date: 2019-08-23
Publication date: 2020-11-26
Also published as: CN110067130A

Abstract

Disclosed is a method for preparing an antibacterial and anti-wrinkle hydrogel, comprising the steps as follows: mixing chitosan and an NaOH solution, sequentially adding isopropanol and 1-chloroguanidine acetic acid for reaction, and adjusting same to be neutral; adding an anhydrous ether and stirring same, filtering same using suction, then drying and grinding same so as to obtain a guanidine acetic acid chitosan; subjecting a suspension containing a nano-cellulose to an ultrasound pretreatment, and adding sodium periodate and an acetic acid-sodium acetate buffer solution for oscillating reaction; adding ethylene glycol and stirring same, and concentrating same after dialysis; subjecting same to an ultrasound pretreatment; adding a silver nitrate solution, adjusting the pH, stirring same for reaction; centrifuging same, and then washing the solid and freeze-drying same; adding an N,N-dimethylacetamide, and heating and stirring same; adding the guanidine acetic acid chitosan and stirring same; subjecting same to aging, immersing same in ethanol, and immersing same in deionized water; immersing same in a mixed solution containing tartaric acid and butane tetracarboxylic dianhydride; immersing same in deionized water; and taking out and drying same to obtain the hydrogel. The antibacterial and anti-wrinkle hydrogel obtained with the present method has good anti-wrinkle and mechanical properties, and also has very good antibacterial properties.

Description

Preparation method of antibacterial and anti-wrinkle hydrogel and its application in textiles

Technical field

The invention relates to a preparation method of an antibacterial and anti-wrinkle hydrogel and its application in textiles.

Background technique

Hydrogel is a gel with water as the dispersion medium, and its skeleton structure is a polymer network system. It can swell in water without dissolving, and hydrophilic small molecules can effectively diffuse in the system. This is mainly because the water-soluble polymer molecular chain with steric cross-linked structure in the hydrogel material contains hydrophobic groups and hydrophilic groups. When the hydrogel is placed in water, the hydrophilic groups in the system combine with water molecules to fix the water molecules inside the system, and the hydrophobic residues will swell the system when exposed to water. The temperature requirement for the reaction of the hydrogel is relatively low, and at the same time, it can make full use of the activeness of the hydroxyl group to crosslink with the textile through a relatively mild chemical reaction to obtain uniform and stable anti-wrinkle performance. It also has broad development prospects in the textile industry.

Summary of the invention

Technical problems to be solved:

Provided is a method for preparing an antibacterial and anti-wrinkle hydrogel. The obtained antibacterial and anti-wrinkle hydrogel has good anti-wrinkle performance and mechanical properties, as well as good antibacterial performance.

Technical solutions:

The invention provides a method for preparing an antibacterial and anti-wrinkle hydrogel. The components are calculated in parts by weight and include the following steps:

(1) Mix 3.5-4 parts of chitosan and 10-15 parts of 50% NaOH solution, then add 20-30 parts of isopropanol and 3-4 parts of 1-proguanidine acetic acid in sequence, and stir to react at room temperature 2-3h;

(2) Heat to 60-70°C, continue to stir and react for 2-3h, cool to room temperature, add glacial acetic acid to adjust to neutral, continue to stir for 10-20min;

(3) Add 20-30 parts of anhydrous diethyl ether and stir, dry the solid after suction filtration, and grind to obtain guanidine acetate chitosan;

(4) The suspension containing 1-2 parts of nanocellulose is ultrasonically pretreated for 5-7 minutes, 1.5-2 parts of sodium periodate and 30-50 parts of acetic acid-sodium acetate buffer solution with pH 3.5 are added, and 150 are added. -200 parts of deionized water, shaking reaction at 45-50℃ for 48-50h;

(5) Add 20-30 parts of ethylene glycol, cool to room temperature and stir for 30-60 minutes, put it in a dialysis bag for one week, and concentrate in a rotary evaporator;

(6) Transfer to a beaker, ultrasonic pretreatment for 10-15 minutes;

(7) Add 5-8 parts of 2g/L silver nitrate solution dropwise, then adjust the pH to 7-9 with sodium hydroxide solution, and stir the reaction at 70°C for 36-40h;

(8) Wash the solid 3-5 times after centrifugation and freeze-dry it;

(9) Add 20-30 parts of N,N-dimethylacetamide, heat and stir;

(10) Add 3-5 parts of guanidine acetic acid chitosan, reduce to room temperature and continue stirring;

(11) Pour into a petri dish and place it at room temperature, age for 20-24 hours, immerse in ethanol, seal and stand for 5-10 hours, take it out and immerse it in deionized water, and leave it for 5-10 hours;

(12) After taking it out, immerse it in a mixed solution containing 5-10wt% tartaric acid and butanetetracarboxylic dianhydride for 10-12h;

(13) Take it out and soak in deionized water for 6-8h;

(14) Take it out and put it in an oven to dry to obtain an antibacterial and anti-wrinkle hydrogel.

Further, the ultrasonic pretreatment in the step (4) is ultrasonic 4s, gap 8s, and power 300W.

Further, the ultrasonic pretreatment in the step (6) is ultrasonic 4s, gap 8s, and power 300W.

Further, in the step (12), the mass ratio of tartaric acid and butanetetracarboxylic dianhydride is 1:1.

Application of the antibacterial and anti-wrinkle hydrogel prepared by the preparation method of the antibacterial and anti-wrinkle hydrogel in textiles.

Benefits:

1. Guanidine acetic acid chitosan has good moisturizing properties. It can form a stable three-dimensional structure with cellulose during the formation of sol-gel to achieve anti-wrinkle effect and also has good antibacterial effect.

2. Tartaric acid and butane tetracarboxylic dianhydride have very good anti-wrinkle effects, especially through cross-linking with cellulose, increasing the average length and branching degree of cross-linking, thereby improving the elasticity of the cross-linking network.

3. The silver ions are reduced to silver element during the reaction. The silver ions continue to grow on the surface of the cellulose, and the aldehyde groups in the cellulose are oxidized to carboxyl groups. The silver ions are gradually formed and attached to the cellulose to achieve antibacterial effects.

4. The antibacterial and anti-wrinkle hydrogel prepared by the method of the present invention has good anti-wrinkle performance and mechanical properties. Its wrinkle recovery angle can reach up to 190.9°, the breaking strength is less than 386.7N, and it also has good antibacterial properties. Both Bacillus and Staphylococcus aureus have good inhibitory effects.

Detailed ways

The following embodiments may enable those skilled in the art to fully understand the present invention, but do not limit the present invention in any way.

Example 1

The preparation method of antibacterial and anti-wrinkle hydrogel includes the following steps:

(1) Mix 3.5 parts of chitosan and 10 parts of 50% NaOH solution, then add 20 parts of isopropanol and 3 parts of 1-proguanidine acetic acid in sequence, and stir for 2h at room temperature;

(2) Heat to 60°C, continue to stir and react for 2h, cool to room temperature, add glacial acetic acid to adjust to neutral, continue to stir for 10min;

(3) Add 20 parts of anhydrous ethyl ether and stir, after suction filtration, dry the solid and grind to obtain guanidine acetate chitosan;

(4) The suspension containing 1 part of nanocellulose was ultrasonically pretreated for 5 minutes, 1.5 parts of sodium periodate and 30 parts of acetic acid-sodium acetate buffer solution with pH 3.5 were added, and 150 parts of deionized water were added at 45°C. Shake down for 48h;

(5) Add 20 parts of ethylene glycol, cool to room temperature and stir for 30 minutes, put it in a dialysis bag for one week, and concentrate on a rotary evaporator;

(6) Transfer to a beaker, ultrasonic pretreatment for 10 minutes;

(7) Add 5 parts of 2g/L silver nitrate solution dropwise, then adjust the pH to 7 with sodium hydroxide solution, and stir the reaction at 70°C for 36h;

(8) Wash the solid 3 times after centrifugation and freeze-dry it;

(9) Add 20 parts of N,N-dimethylacetamide, heat and stir;

(10) Add 3 parts of guanidine acetic acid chitosan, reduce to room temperature and continue stirring;

(11) Pour into a petri dish and place it at room temperature, age for 20 hours, immerse in ethanol, seal and stand for 5 hours, take it out and immerse it in deionized water, and stand for 5 hours;

(12) After taking it out, immerse it in a mixed solution containing 5wt% tartaric acid and butanetetracarboxylic dianhydride for 10h;

(13) Take it out and immerse it in deionized water for 6 hours;

Example 2

(1) Mix 3.7 parts of chitosan and 12 parts of 50% NaOH solution, then add 23 parts of isopropanol and 3.3 parts of 1-proguanidine acetic acid in sequence, and stir for 2.5 hours at room temperature;

(2) Heat to 65°C, continue to stir and react for 2.5 hours, cool to room temperature, add glacial acetic acid to adjust to neutral, and continue stirring for 15 minutes;

(3) Add 23 parts of anhydrous ethyl ether and stir, after suction filtration, dry the solid and grind to obtain guanidine acetate chitosan;

(4) The suspension containing 1.3 parts of nanocellulose was ultrasonically pretreated for 6 minutes, 1.7 parts of sodium periodate and 35 parts of acetic acid-sodium acetate buffer solution with pH 3.5 were added, and 170 parts of deionized water were added at 45°C. 48.5h under shaking reaction;

(5) Add 23 parts of ethylene glycol, cool to room temperature and stir for 40 minutes, put it in a dialysis bag for one week, and concentrate on a rotary evaporator;

(6) Transfer to a beaker, ultrasonic pretreatment for 12 minutes;

(7) Add 6 parts of 2g/L silver nitrate solution dropwise, then adjust the pH to 8 with sodium hydroxide solution, and stir the reaction at 70°C for 37h;

(8) Wash the solid 4 times after centrifugation and freeze-dry it;

(9) Add 23 parts of N,N-dimethylacetamide, heat and stir;

(10) Add 3.5 parts of guanidine acetic acid chitosan, reduce to room temperature and continue stirring;

(11) Pour into a petri dish and place it at room temperature, age for 1 hour, immerse in ethanol, seal and stand for 7 hours, take it out and immerse it in deionized water, and stand for 7 hours;

(12) After taking it out, immerse it in a mixed solution containing 7wt% tartaric acid and butanetetracarboxylic dianhydride for 10.5h;

(13) Take it out and immerse it in deionized water for 6.5h;

Example 3

(1) Mix 3.8 parts of chitosan and 13 parts of 50% NaOH solution, then add 25 parts of isopropanol and 3.5 parts of 1-proguanidine acetic acid in sequence, and stir for 2.5 hours at room temperature;

(3) Add 25 parts of anhydrous ethyl ether and stir, after suction filtration, dry the solid and grind to obtain guanidine acetate chitosan;

(4) The suspension containing 1.5 parts of nanocellulose was ultrasonically pretreated for 6 minutes, 1.8 parts of sodium periodate and 40 parts of acetic acid-sodium acetate buffer solution with pH 3.5 were added, and 180 parts of deionized water were added at 45°C. Lower shaking reaction for 49h;

(5) Add 25 parts of ethylene glycol, cool to room temperature and stir for 45 minutes, put it into a dialysis bag for one week, and concentrate on a rotary evaporator;

(6) Transfer to a beaker and ultrasonic pretreatment for 13 minutes;

(7) Add 5-8 parts of 2g/L silver nitrate solution dropwise, then adjust the pH to 8 with sodium hydroxide solution, and stir the reaction at 70°C for 38h;

(8) Wash the solid 4 times after centrifugation and freeze-dry it;

(9) Add 25 parts of N,N-dimethylacetamide, heat and stir;

(10) Add 4 parts of guanidine acetic acid chitosan, reduce to room temperature and continue stirring;

(11) Pour into a petri dish and place it at room temperature, age for 22 hours, immerse in ethanol, seal and stand for 8 hours, take it out and immerse it in deionized water, and leave it for 8 hours;

(12) After taking it out, immerse it in a mixed solution containing 8wt% tartaric acid and butanetetracarboxylic dianhydride for 11h;

(13) Take it out and immerse it in deionized water for 7 hours;

Example 4

(1) Mix 3.9 parts of chitosan and 14 parts of 50% NaOH solution, then sequentially add 28 parts of isopropanol and 3.5 parts of 1-proguanidine acetic acid, and stir for 2.5 hours at room temperature;

(3) Add 28 parts of anhydrous ethyl ether and stir, after suction filtration, dry the solid and grind to obtain guanidine acetate chitosan;

(4) The suspension containing 1.8 parts of nanocellulose was ultrasonically pretreated for 6 minutes, 1.9 parts of sodium periodate and 45 parts of acetic acid-sodium acetate buffer solution with pH 3.5 were added, and 190 parts of deionized water were added at 50°C. Lower shaking reaction for 49h;

(5) Add 28 parts of ethylene glycol, cool to room temperature and stir for 50 minutes, put it in a dialysis bag for one week, and concentrate on a rotary evaporator;

(6) Transfer to a beaker and ultrasonic pretreatment for 14 minutes;

(7) Add 7 parts of 2g/L silver nitrate solution dropwise, then adjust the pH to 8 with sodium hydroxide solution, and stir the reaction at 70°C for 39h;

(8) Wash the solid 4 times after centrifugation and freeze-dry it;

(9) Add 28 parts of N,N-dimethylacetamide, heat and stir;

(10) Add 4.5 parts of guanidine acetic acid chitosan, reduce to room temperature and continue stirring;

(11) Pour into a petri dish and place it at room temperature, age for 23 hours, immerse in ethanol, seal and stand for 9 hours, take it out and immerse it in deionized water and leave it for 9 hours;

(12) After taking it out, immerse it in a mixed solution containing 9wt% tartaric acid and butanetetracarboxylic dianhydride for 11h;

(13) Take it out and soak in deionized water for 9h;

Example 5

(1) Mix 4 parts of chitosan and 15 parts of 50% NaOH solution, then add 30 parts of isopropanol and 4 parts of 1-proguanidine acetic acid in sequence, and stir and react at room temperature for 3 hours;

(2) Heat to 70°C, continue to stir and react for 3 hours, cool to room temperature, add glacial acetic acid to adjust to neutral, and continue stirring for 20 minutes;

(3) Add 30 parts of anhydrous ethyl ether and stir, after suction filtration, dry the solid and grind to obtain guanidine acetate chitosan;

(4) The suspension containing 2 parts of nanocellulose was ultrasonically pretreated for 7 minutes, and 2 parts of sodium periodate and 50 parts of acetic acid-sodium acetate buffer solution with pH 3.5 were added, and 200 parts of deionized water were added at 50°C. Shake down for 50h;

(5) Add 30 parts of ethylene glycol, cool to room temperature and stir for 60 minutes, put it into a dialysis bag for one week, and concentrate on a rotary evaporator;

(6) Transfer to a beaker, ultrasonic pretreatment 15mm;

(7) Add 8 parts of 2g/L silver nitrate solution dropwise, then adjust the pH to 9 with sodium hydroxide solution, and stir and react at 70°C for 40h;

(8) Wash the solid 5 times after centrifugation and freeze-dry it;

(9) Add 30 parts of N,N-dimethylacetamide, heat and stir;

(10) Add 5 parts of guanidine acetic acid chitosan, reduce to room temperature and continue stirring;

(11) Pour into a petri dish and place at room temperature, aging for 24 hours, immerse in ethanol, seal and stand for 10 hours, take it out and immerse in deionized water, and leave for 10 hours;

(12) After taking it out, immerse it in a mixed solution containing 10wt% tartaric acid and butanetetracarboxylic dianhydride for 12h;

(13) Take it out and soak in deionized water for 8 hours;

The hydrogel of the present invention is formulated into a finishing agent with an amount of 10%.

Room temperature padding finishing solution (two padding and two rolling, rolling residual rate 100%) → pre-baking (80°C, 5min) → baking (170-180°C, 1-3min) → washing (60°C, 15min) → drying (80-85°C).

Wrinkle recovery angle: Measured according to GB/T 3819-1997 "Determination of Recovery Angle Method for Textile Fabric Crease Recovery".

Breaking strength: According to the strip test method in GB/T 3923.1-1997 "Textile Fabric Tensile Properties", use an electronic fabric strength meter to test the breaking strength of the finished fabric.

Table 1 Antibacterial and anti-wrinkle properties of antibacterial and anti-wrinkle hydrogel

The anti-bacterial anti-wrinkle hydrogel prepared by the method of the present invention has good anti-wrinkle performance and mechanical properties, its wrinkle recovery angle can reach up to 190.9°, the breaking strength is less than 386.7N, and it also has good antibacterial properties. Staphylococcus aureus has a good inhibitory effect.

Claims

The preparation method of the antibacterial and anti-wrinkle hydrogel is characterized in that the components are calculated in parts by weight and include the following steps:

(1) Mix 3.5-4 parts of chitosan and 10-15 parts of 50% NaOH solution, then add 20-30 parts of isopropanol and 3-4 parts of 1-proguanidine acetic acid in sequence, and stir to react at room temperature 2-3h;

(2) Heat to 60-70°C, continue to stir and react for 2-3h, cool to room temperature, add glacial acetic acid to adjust to neutral, continue to stir for 10-20min;

(3) Add 20-30 parts of anhydrous diethyl ether and stir, dry the solid after suction filtration, and grind to obtain guanidine acetate chitosan;

(4) The suspension containing 1-2 parts of nanocellulose is ultrasonically pretreated for 5-7 minutes, 1.5-2 parts of sodium periodate and 30-50 parts of acetic acid-sodium acetate buffer solution with pH 3.5 are added, and 150 are added. -200 parts of deionized water, shaking reaction at 45-50℃ for 48-50h;

(5) Add ethylene glycol, stir for 30-60min at room temperature, put it in a dialysis bag for one week, and concentrate in a rotary evaporator;

(6) Transfer to a beaker, ultrasonic pretreatment for 10-15 minutes;

(7) Add 2g/L silver nitrate solution drop by drop, then adjust the pH to 7-9 with sodium hydroxide solution, stir and react at 70°C for 36-40h;

(8) Wash the solid 3-5 times after centrifugation and freeze-dry it;

(9) Add N,N-dimethylacetamide, heat and stir;

(10) Add 3-5 parts of guanidine acetic acid chitosan, reduce to room temperature and continue stirring;

(11) Pour into a petri dish and place it at room temperature, age for 20-24 hours, immerse in ethanol, seal and stand for 5-10 hours, take it out and immerse it in deionized water, and leave it for 5-10 hours;

(12) After taking it out, immerse it in a mixed solution containing 5-10wt% tartaric acid and butanetetracarboxylic dianhydride for 10-12h;

(13) Take it out and soak in deionized water for 6-8h;

(14) Take it out and put it in an oven to dry to obtain an antibacterial and anti-wrinkle hydrogel.
The preparation method of the antibacterial and anti-wrinkle hydrogel according to claim 1, wherein the ultrasonic pretreatment in the step (4) is ultrasonic 4s, gap 8s, and power 300W.
The preparation method of the antibacterial and anti-wrinkle hydrogel according to claim 1, wherein the ultrasonic pretreatment in the step (6) is ultrasonic 4s, gap 8s, and power 300W.
The method for preparing antibacterial and anti-wrinkle hydrogel according to claim 1, wherein the mass ratio of tartaric acid and butanetetracarboxylic dianhydride in the step (12) is 1:1.
Application of the antibacterial and anti-wrinkle hydrogel prepared by the method for preparing the antibacterial and anti-wrinkle hydrogel according to claims 1-4 in textiles.