1. A preparation method of a modified grafted hydrophilic flexible polyester fabric is characterized by comprising the following steps:

s1, modifying polyester fibers by using alkali amine: placing the polyester fabric in mixed finishing liquid of ethylenediamine and sodium hydroxide, and carrying out surface modification on the polyester fabric at a certain bath ratio;

s2, preparing a pre-reaction solution: mixing polyvinyl alcohol ester, water, ammonia water and a silane coupling agent according to a certain proportion to obtain hydrophilic modification pre-reaction liquid;

s3, grafting modification of the polyester fabric: soaking the polyester fabric prepared in the step S1 in ethanol, soaking in a pre-reaction solution, reacting at a certain temperature, and adjusting the pH value to 3-4 to obtain a polyester fabric with the surface grafted and modified;

s4, preparing the flexible polyester fabric: and (3) soaking the polyester fabric prepared in the last step in a glutaraldehyde aqueous solution, taking out the polyester fabric after soaking to remove residual glutaraldehyde, then placing the polyester fabric in a small molecule polypeptide solution for reaction, taking out the polyester fabric, cleaning and drying the polyester fabric to obtain the hydrophilic flexible polyester fabric.

2. The preparation method of the modified grafted hydrophilic polyester fabric according to claim 1, characterized in that: the concentration of ethylenediamine in the finishing liquid is 1-3%, the concentration of sodium hydroxide is 5.5-12%, and the bath ratio is 1: 20-40 deg.C at 60-70 deg.C for 60-90 min.

3. The preparation method of the modified grafted hydrophilic polyester fabric according to claim 1, characterized in that: the silane coupling agent is an aminosilane coupling agent.

4. The preparation method of the modified grafted hydrophilic polyester fabric according to claim 1, characterized in that: the pH value of the pre-reaction liquid is maintained at 7-8, and the ratio of the polyvinyl alcohol ester to the silane coupling agent to the water is 1:0.5-2: 100.

5. The preparation method of the modified grafted hydrophilic polyester fabric according to claim 1, characterized in that: the reaction temperature is that the reaction is carried out for 30min at 40-50 ℃, and then the temperature is raised to 70-80 ℃ for reaction for 4-7 h.

6. The preparation method of the modified grafted hydrophilic polyester fabric according to claim 1, characterized in that: the concentration of the glutaraldehyde solution is 20-30 wt%, the soaking time is 30-60min, and the temperature is 50-80 ℃.

7. The preparation method of the modified grafted hydrophilic polyester fabric according to claim 1, characterized in that: the small molecule polypeptide solution is degraded from fibroin or sericin, and the concentration of the small molecule polypeptide solution is 0.5-3.5 wt%.

Background

Polyester has good crease elasticity and stiffness, and is widely used as textile garment fabrics and other industrial fiber products. However, because only two hydroxyl groups are arranged at two ends of the polyester macromolecule, the polyester fabric is hydrophobic, does not absorb moisture and conduct moisture, and has poor wearing comfort and biocompatibility. Hydrophilic modification of polyester fabrics is always a hot topic of polyester modification.

At present, terylene is applied in mass production due to excellent mechanical properties, but terylene has compact molecular structure, high crystallinity, relatively poor hydrophilicity and moisture absorption performance, so that the application field of terylene is correspondingly limited. In order to improve the hydrophilic performance of terylene, a great deal of research has been carried out in China and abroad for many years, and the adopted hydrophilic modification method is mainly divided into two types: firstly, polyester fiber raw materials are modified, the method has high technical requirements, and the method is less in application in actual production; and secondly, hydrophilic modification is carried out on the surface of the polyester fiber, and the methods of introducing hydrophilic substances into the surface of the fiber and the like are mainly adopted, so that the process is simple and the operation is convenient.

The polyester fabric has good stiffness, good crease elasticity and can be washed and worn; the fibroin has good biocompatibility, is friendly to human skin and has a health-care function; therefore, the research on grafting the silk protein on the surface of the polyester fabric and developing the high-function polyester fabric with good wearability and good biocompatibility have important significance.

Disclosure of Invention

The technical problem to be solved is as follows: the invention aims to provide a modified grafted hydrophilic flexible polyester fabric, solves the problem of poor hydrophilicity of the existing polyester, simultaneously researches on grafting silk fibroin on the surface of a polyester fabric, and develops a high-function polyester fabric with good wearability and good biocompatibility.

The technical scheme is as follows: a preparation method of a modified grafted hydrophilic flexible polyester fabric comprises the following steps:

s1, modifying polyester fibers by using alkali amine: placing the polyester fabric in mixed finishing liquid of ethylenediamine and sodium hydroxide, and carrying out surface modification on the polyester fabric at a certain bath ratio;

s2, preparing a pre-reaction solution: mixing polyvinyl alcohol ester, water, ammonia water and a silane coupling agent according to a certain proportion to obtain hydrophilic modification pre-reaction liquid;

s3, grafting modification of the polyester fabric: soaking the polyester fabric prepared in the step S1 in ethanol, soaking in a pre-reaction solution, reacting at a certain temperature, and adjusting the pH value to 3-4 to obtain a polyester fabric with the surface grafted and modified;

s4, preparing the flexible polyester fabric: and (3) soaking the polyester fabric prepared in the last step in a glutaraldehyde aqueous solution, taking out the polyester fabric after soaking to remove residual glutaraldehyde, then placing the polyester fabric in a small molecule polypeptide solution for reaction, taking out the polyester fabric, cleaning and drying the polyester fabric to obtain the hydrophilic flexible polyester fabric.

Preferably, the concentration of ethylenediamine in the finishing liquid is 1-3%, the concentration of sodium hydroxide is 5.5-12%, the bath ratio is 1: 20-40 deg.C at 60-70 deg.C for 60-90 min.

Preferably, the silane coupling agent is an aminosilane coupling agent.

Preferably, the aminosilane coupling agent is

Preferably, the pH value in the pre-reaction liquid is maintained to be 7-8, and the ratio of the polyvinyl alcohol ester to the silane coupling agent to the water is 1:0.5-2: 100.

Preferably, the reaction temperature is that the reaction is firstly carried out for 30min at 40-50 ℃, and then the temperature is raised to 70-80 ℃ for reaction for 4-7 h.

Preferably, the concentration of the glutaraldehyde solution is 20-30 wt%, the soaking time is 30-60min, and the temperature is 50-80 ℃.

Preferably, the small molecule polypeptide solution is a small molecule polypeptide solution degraded by fibroin or sericin, and the concentration of the small molecule polypeptide solution is 0.5-3.5 wt%.

Has the advantages that: the invention has the following advantages:

1. selecting polyvinyl alcohol ester and an aminosilane coupling agent, and coating a hydrophilic layer containing a large number of carboxyl and silicon hydroxyl on the surface of the polyester fabric by a crosslinking method to endow the polyester fabric with stable hydrophilicity;

2. the wearability of the hydrophilic polyester fabric modified by grafting is reduced, and then the micromolecular silk protein peptide is grafted on the surface of the polyester fabric to prepare the high-functional polyester fabric with good wearability and good hydrophilicity.

Detailed Description

Example 1

A preparation method of a modified grafted hydrophilic flexible polyester fabric comprises the following steps:

s1, modifying polyester fibers by using alkali amine: placing the polyester fabric in mixed finishing liquid of ethylenediamine and sodium hydroxide, wherein the concentration of the ethylenediamine in the finishing liquid is 1%, the concentration of the sodium hydroxide in the finishing liquid is 5.5%, and the bath ratio is 1: performing surface modification on the polyester fabric at the temperature of 60 ℃ for 90min under 20 ℃;

s2, preparing a pre-reaction solution: mixing polyvinyl alcohol ester, water, ammonia water and an aminosilane coupling agent according to a certain ratio, wherein the ratio of the polyvinyl alcohol ester to the silane coupling agent to the water is 1:0.5:100, and obtaining hydrophilic modification pre-reaction liquid;

s3, grafting modification of the polyester fabric: soaking the polyester fabric prepared in the step S1 in ethanol, soaking in a pre-reaction solution, reacting at 40 ℃ for 30min, heating to 70 ℃ for reacting for 4h, and adjusting the pH value to 4 to obtain the polyester fabric with the surface grafted and modified;

s4, preparing the flexible polyester fabric: and (3) soaking the polyester fabric prepared in the last step in a glutaraldehyde aqueous solution with the concentration of 20 wt%, wherein the soaking time is 30min and the temperature is 50 ℃, taking out the polyester fabric after soaking to remove residual glutaraldehyde, then placing the polyester fabric in a small molecule polypeptide solution for reaction, wherein the concentration of the glutaraldehyde is 0.5 wt%, taking out the polyester fabric, cleaning and drying the polyester fabric to obtain the hydrophilic flexible polyester fabric.

Example 2

A preparation method of a modified grafted hydrophilic flexible polyester fabric comprises the following steps:

s1, modifying polyester fibers by using alkali amine: placing the polyester fabric in mixed finishing liquid of ethylenediamine and sodium hydroxide, wherein the concentration of the ethylenediamine in the finishing liquid is 3%, the concentration of the sodium hydroxide in the finishing liquid is 12%, and the ratio of bath to bath is 1: carrying out surface modification on the polyester fabric at the temperature of 70 ℃ for 60min under 40 ℃;

s2, preparing a pre-reaction solution: mixing polyvinyl alcohol ester, water, ammonia water and an aminosilane coupling agent in a certain ratio, wherein the ratio of the polyvinyl alcohol ester to the silane coupling agent to the water is 1:2:100, and obtaining hydrophilic modification pre-reaction liquid;

s3, grafting modification of the polyester fabric: soaking the polyester fabric prepared in the step S1 in ethanol, soaking in a pre-reaction solution, reacting at 50 ℃ for 30min, heating to 80 ℃ for reaction for 7h, and adjusting the pH value to 3 to obtain a polyester fabric with the surface grafted and modified;

s4, preparing the flexible polyester fabric: and (3) soaking the polyester fabric prepared in the last step in a glutaraldehyde aqueous solution with the concentration of 30 wt%, wherein the soaking time is 60min and the temperature is 80 ℃, taking out the polyester fabric after soaking to remove residual glutaraldehyde, then placing the polyester fabric in a small molecule polypeptide solution for reaction, wherein the concentration of the glutaraldehyde is 3.5 wt%, taking out the polyester fabric, cleaning and drying the polyester fabric to obtain the hydrophilic flexible polyester fabric.

Example 3

A preparation method of a modified grafted hydrophilic flexible polyester fabric comprises the following steps:

s1, modifying polyester fibers by using alkali amine: placing the polyester fabric in mixed finishing liquid of ethylenediamine and sodium hydroxide, wherein the concentration of the ethylenediamine in the finishing liquid is 1.5%, the concentration of the sodium hydroxide in the finishing liquid is 7%, and the ratio of bath to bath is 1: carrying out surface modification on the polyester fabric at the temperature of 65 ℃ for 60min under 25 ℃;

s2, preparing a pre-reaction solution: mixing polyvinyl alcohol ester, water, ammonia water and an aminosilane coupling agent according to a certain ratio, wherein the ratio of the polyvinyl alcohol ester to the silane coupling agent to the water is 1:0.8:100, and obtaining hydrophilic modification pre-reaction liquid;

s3, grafting modification of the polyester fabric: soaking the polyester fabric prepared in the step S1 in ethanol, soaking in a pre-reaction solution, reacting at 42 ℃ for 30min, heating to 74 ℃ for reaction for 5h, and adjusting the pH value to 4 to obtain a polyester fabric with the surface grafted and modified;

s4, preparing the flexible polyester fabric: and (3) soaking the polyester fabric prepared in the last step in a glutaraldehyde aqueous solution with the concentration of 22 wt%, wherein the soaking time is 40min and the temperature is 60 ℃, taking out the polyester fabric after soaking to remove residual glutaraldehyde, then placing the polyester fabric in a small molecule polypeptide solution for reaction, wherein the concentration of the glutaraldehyde is 1.8 wt%, taking out the polyester fabric, cleaning and drying the polyester fabric to obtain the hydrophilic flexible polyester fabric.

Example 4

A preparation method of a modified grafted hydrophilic flexible polyester fabric comprises the following steps:

s1, modifying polyester fibers by using alkali amine: placing the polyester fabric in mixed finishing liquid of ethylenediamine and sodium hydroxide, wherein the concentration of the ethylenediamine in the finishing liquid is 2.5%, the concentration of the sodium hydroxide in the finishing liquid is 10%, and the ratio of bath to bath is 1: at the temperature of 70 ℃ for 90min, carrying out surface modification on the polyester fabric at 35 ℃;

s2, preparing a pre-reaction solution: mixing polyvinyl alcohol ester, water, ammonia water and an aminosilane coupling agent according to a certain ratio, wherein the ratio of the polyvinyl alcohol ester to the silane coupling agent to the water is 1:1.5:100, and obtaining hydrophilic modification pre-reaction liquid;

s3, grafting modification of the polyester fabric: soaking the polyester fabric prepared in the step S1 in ethanol, soaking in a pre-reaction solution, reacting at 46 ℃ for 30min, heating to 78 ℃ for reacting for 6h, and adjusting the pH value to 3 to obtain a polyester fabric with the surface grafted and modified;

s4, preparing the flexible polyester fabric: and (3) soaking the polyester fabric prepared in the last step in a glutaraldehyde aqueous solution with the concentration of 26 wt%, wherein the soaking time is 50min and the temperature is 70 ℃, taking out the polyester fabric after soaking to remove residual glutaraldehyde, then placing the polyester fabric in a small molecule polypeptide solution for reaction, wherein the concentration of the glutaraldehyde is 3 wt%, taking out, cleaning and airing the polyester fabric to obtain the hydrophilic flexible polyester fabric.

Example 5

A preparation method of a modified grafted hydrophilic flexible polyester fabric comprises the following steps:

s1, modifying polyester fibers by using alkali amine: placing the polyester fabric in a mixed finishing liquid of ethylenediamine and sodium hydroxide, wherein the concentration of the ethylenediamine in the finishing liquid is 2%, the concentration of the sodium hydroxide in the finishing liquid is 9%, and the ratio of bath to bath is 1: carrying out surface modification on the polyester fabric at the temperature of 69 ℃ for 70min under 30 ℃;

s2, preparing a pre-reaction solution: mixing polyvinyl alcohol ester, water, ammonia water and an aminosilane coupling agent according to a certain ratio, wherein the ratio of the polyvinyl alcohol ester to the silane coupling agent to the water is 1:1.2:100, and obtaining hydrophilic modification pre-reaction liquid;

s3, grafting modification of the polyester fabric: soaking the polyester fabric prepared in the step S1 in ethanol, soaking in a pre-reaction solution, reacting at 45 ℃ for 30min, heating to 75 ℃ for reaction for 5.5h, and adjusting the pH value to 4 to obtain a polyester fabric with the surface grafted and modified;

s4, preparing the flexible polyester fabric: and (3) soaking the polyester fabric prepared in the last step in a glutaraldehyde aqueous solution with the concentration of 22 wt%, wherein the soaking time is 45min and the temperature is 65 ℃, taking out the polyester fabric after soaking to remove residual glutaraldehyde, then placing the polyester fabric in a small molecule polypeptide solution for reaction, wherein the concentration of the glutaraldehyde is 2.3 wt%, taking out the polyester fabric, cleaning and drying the polyester fabric to obtain the hydrophilic flexible polyester fabric.

Comparative example 1

A preparation method of a modified grafted hydrophilic flexible polyester fabric comprises the following steps:

s1, modifying polyester fibers by using alkali amine: placing the polyester fabric in mixed finishing liquid of ethylenediamine and sodium hydroxide, wherein the concentration of the ethylenediamine in the finishing liquid is 1.5%, the concentration of the sodium hydroxide in the finishing liquid is 7%, and the ratio of bath to bath is 1: carrying out surface modification on the polyester fabric at the temperature of 65 ℃ for 60min under 25 ℃;

s2, preparing a pre-reaction solution: mixing polyvinyl alcohol ester, water, ammonia water and an aminosilane coupling agent according to a certain ratio, wherein the ratio of the polyvinyl alcohol ester to the silane coupling agent to the water is 1:0.8:100, and obtaining hydrophilic modification pre-reaction liquid;

s3, grafting modification of the polyester fabric: and (4) soaking the polyester fabric prepared in the step (S1) in ethanol, soaking in the pre-reaction solution, reacting at 42 ℃ for 30min, heating to 74 ℃ for reaction for 5h, and adjusting the pH value to 4 to obtain the hydrophilic flexible polyester fabric.

Comparative example 2

A preparation method of a modified grafted hydrophilic flexible polyester fabric comprises the following steps:

s1, modifying polyester fibers by using alkali amine: placing the polyester fabric in mixed finishing liquid of ethylenediamine and sodium hydroxide, wherein the concentration of the ethylenediamine in the finishing liquid is 2.5%, the concentration of the sodium hydroxide in the finishing liquid is 10%, and the ratio of bath to bath is 1: at the temperature of 70 ℃ for 90min, carrying out surface modification on the polyester fabric at 35 ℃;

s2, preparing a hydrophilic polyester fabric: and (3) placing the polyester fabric prepared in the last step into a small molecule polypeptide solution for reaction, wherein the concentration of the polyester fabric is 3 wt%, taking out, cleaning and airing to obtain the hydrophilic flexible polyester fabric.

And (3) capillary effect testing: and (3) testing the comprehensive capillary effect value of each sample by using an LFY-215 type fabric capillary effect instrument, wherein the width of each sample is 2.5cm, the length of each sample is 30cm, and each group of samples are tested in the warp direction and the weft direction respectively. Pouring 3000mL of distilled water into a fabric capillary effect instrument, clamping one end of a sample on a sample rack, clamping a tension clamp (3g) at the other end (a drooping end) of the sample, straightening the strip, and ensuring that the longitudinal center line of the sample passes through the center line of a clamp; and adjusting the height of the clamp to enable one end of the sample to be just immersed on the liquid level, timing from the moment when the sample is wetted, and testing the conduction distance of the liquid in the sample after 30min to obtain the average capillary effect value of the warp direction and the weft direction of each group of samples. The test conditions are relative humidity (65 +/-5)%, distilled water temperature (20 +/-3) ° C;

and (3) moisture permeability comprehensive value testing: and flatly paving the sample on a sample rack to keep the sample flat, and suspending the test part. Dripping 40uL of distilled water at a distance of 10cm from the upper part of the sample under the environmental conditions of relative humidity (65 +/-5)%, and temperature (20 +/-3) ° C, measuring the transverse maximum diffusion length a and the longitudinal maximum diffusion length b of the liquid on the dripping surface of the fabric after 3min, testing each group of samples for 5 times, and averaging to obtain the moisture permeability comprehensive value Z which is 0.5(S multiplied by V multiplied by 10)^-1+V×G×10^-3) Wherein the moisture-transmitting area S ═ pi ab/4 (cm)²) Wet permeability V ═ S × H (mm)³) Moisture permeability G ═ S × G × 10^-4(mg/cm²) H is the fabric thickness (mm), g is the fabric areal density;

bending rigidity: testing by using a slope method;

the drape coefficient was measured on a YG811 Fabric drape tester.