A method for preparing a protein hollow conductive fiber

Abstract

The application discloses a preparation method of a protein hollow conductive fiber, which comprises the following steps: adding a covalent organic framework precursor in a protein dissolving process, then spinning the covalent organic framework precursor into a hollow protein wet fiber through a dry-wet method, and generating the covalent organic framework in situ on the fiber surface and the inner wall of the cavity to obtain the protein hollow conductive fiber. The application realizes efficient preparation of the protein hollow conductive fiber, and the prepared protein hollow conductive fiber has high conductivity and good stability, and can be used as a strain sensor for motion monitoring.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of textile materials, and particularly relates to a preparation method of protein hollow conductive fiber. BACKGROUND

[0002] Protein fiber is soft and comfortable to wear, and is popular, but traditional regenerated protein fiber has single function and limited application. The prepared regenerated silk is complex in preparation process and high in cost, and the mechanical property of the regenerated silk is far inferior to that of natural silk. Therefore, developing new functional protein fiber is of great significance for promoting the development of textile materials.

[0003] The unique hollow structure of hollow fiber can endow textiles with some special functional properties, and if protein fiber is made into hollow fiber, the performance advantages of both can be fully utilized to obtain new protein hollow fiber with functional properties. The nanopore channel structure of two-dimensional covalent organic framework can provide a transmission channel for high-speed ion transmission, and therefore, anchoring the covalent organic framework to the surface or inner wall of the hollow protein fiber can endow the hollow protein fiber with conductive ability, so that it can be applied to the field of sensors. SUMMARY

[0004] In view of the problems of single function and limited application of existing protein fiber, the application provides a preparation method of protein hollow conductive fiber.

[0005] To achieve the above-mentioned purpose, the application adopts the following technical scheme:

[0006] A protein hollow conductive fiber, and a preparation method thereof includes the following steps:

[0007] (1) uniformly mixing a n-octanoic acid solution of tri-aldehyde-based phloroglucinol with hexafluoroisopropanol, adding protein, and reacting at 25-50 DEG C for 1-5 h to form a protein solution;

[0008] (2) vacuum deaerating the protein solution obtained in step (1) and spinning to form a hollow protein wet fiber;

[0009] (3) sequentially washing the hollow protein wet fiber spun in step (2) with ethanol, water, and vacuum drying at room temperature, then placing it in a 2,5-diamino-1,4-benzenedisulfonic acid solution, reacting for a certain time in an air-tight manner to in-situ generate covalent organic framework on the surface and inner wall of the hollow protein fiber, and then washing with water and vacuum drying to form the protein hollow conductive fiber.

[0010] Further, the protein in step (1) is any one of keratin, collagen, and glutenin.

[0011] Further, the dosage ratio of the protein to the n-octanoic acid solution of tri-aldehyde phloroglucinol and hexafluoroisopropanol in step (1) is 2g:5-10mL:10mL; the concentration of the n-octanoic acid solution of tri-aldehyde phloroglucinol is 5-7.5mmol / L.

[0012] Further, the hollow protein wet fiber in step (2) is specifically prepared by dry-wet spinning of the protein solution under the conditions of a pressure of 0.6MPa and a temperature of 50 DEG C by using a coaxial spinneret.

[0013] Further, the dosage ratio of the hollow protein wet fiber to the 2,5-diamino-1,4-benzenedisulfonic acid solution in step (3) is 1g:25-50mL; the concentration of the 2,5-diamino-1,4-benzenedisulfonic acid solution is 4-6mmol / L.

[0014] Further, the temperature of the reaction in step (3) is 50-60 DEG C, and the time is 80-100h.

[0015] The present application has the advantages that:

[0016] The present application has the advantages that:

[0017] The present application has the advantages that: BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 A schematic diagram for LED light lighting test by using the protein hollow conductive fiber obtained in Example 1;

[0019] Figure 2 A graph showing the resistance change of the protein hollow conductive fiber obtained in Example 2 when used as a strain sensor to test the wrist joint movement;

[0020] Figure 3 A graph showing the resistance change of the protein hollow conductive fiber obtained in Example 3 when used as a strain sensor to test the knee joint movement. DETAILED DESCRIPTION

[0021] A protein hollow conductive fiber, a preparation method thereof comprises the following steps:

[0022] (1) uniformly mixing a 5-7.5 mmol / L triketo-phloroglucinol n-octanoic acid solution with hexafluoroisopropanol, and adding a protein, so that the ratio of the protein to the triketo-phloroglucinol n-octanoic acid solution and the hexafluoroisopropanol is 2 g:5-10 mL:10 mL, and then reacting at 25-50°C for 1-5 h to form a protein solution;

[0023] (2) vacuum degassing the protein solution obtained in step (1), and then performing dry-wet spinning (with ethanol as a coagulation bath) under the conditions of a pressure of 0.6 MPa and a temperature of 50°C to obtain a hollow protein wet fiber;

[0024] (3) sequentially washing the spun hollow protein wet fiber with ethanol, washing with water, and vacuum drying at room temperature, then placing 1 g of the hollow protein fiber in 25-50 mL of a 4-6 mmol / L 2,5-diamino-1,4-benzenedisulfonic acid solution, and reacting at 50-60°C in an air-tight manner for 80-100 h to in-situ form a covalent organic framework on the surface and the cavity inner wall of the hollow protein fiber, and then washing with water and vacuum drying to obtain the protein hollow conductive fiber.

[0025] In step (1), the protein is any one of keratin, collagen, and gliadin.

[0026] In order to make the content of the application more convenient to understand, the technical solutions of the application will be further described below in combination with specific embodiments, but the application is not limited thereto.

[0027] Example 1

[0028] (1) taking 6 g of keratin, and adding the keratin into a mixed solution composed of 30 mL of a 5 mmol / L triketo-phloroglucinol n-octanoic acid solution and 30 mL of hexafluoroisopropanol, and stirring and reacting at 50°C for 1 h to form a protein solution;

[0029] (2) vacuum degassing the protein solution, and then performing dry-wet spinning (with ethanol as a coagulation bath) under the conditions of a pressure of 0.6 MPa and a temperature of 50°C to form a hollow protein wet fiber;

[0030] (3) sequentially washing the spun hollow protein wet fiber with ethanol, washing with water, and vacuum drying at room temperature, then placing 3 g of the hollow protein fiber into 150 mL of a 4 mmol / L 2,5-diamino-1,4-benzenedisulfonic acid solution, and reacting at 60°C in an air-tight manner for 80 h to in-situ form a covalent organic framework on the surface and the cavity inner wall of the hollow protein fiber, and then washing with water and vacuum drying to obtain the protein hollow conductive fiber.

[0031] A bundle of the protein hollow conductive fibers was taken to carry out the LED light lighting test, as shown in Figure 1 .

[0032] Example 2

[0033] (1) 4 g of collagen protein was taken and added to a mixed solution composed of 10 mL of 7.5 mmol / L tri-aldehyde m-benzene triol n-octanoic acid solution and 20 mL of hexafluoroisopropanol, and stirred at 30°C for 5 h to form a protein solution;

[0034] (2) After the protein solution was vacuum degassed, dry-wet spinning was carried out under the conditions of a pressure of 0.6 MPa and a temperature of 50°C using a coaxial spinneret (with ethanol as a coagulation bath for solidification and molding) to form a hollow protein wet fiber;

[0035] (3) After the spun hollow protein wet fiber was sequentially washed with ethanol, washed with water, and vacuum dried at room temperature, 2 g of the hollow protein fiber was placed in 50 mL of a 2,5-diamino-1,4-benzene disulfonic acid solution with a concentration of 6 mmol / L, and reacted at 50°C for 100 h in an air-tight manner to generate a covalent organic framework in situ on the surface and the inner wall of the hollow protein fiber, and then washed with water and vacuum dried to obtain a protein hollow conductive fiber.

[0036] A bundle of the protein hollow conductive fibers was taken to carry out the LED light lighting test, as shown in Figure 2 . As can be seen from Figure 2 , the relative resistance value of the conductive wire composed of the protein hollow conductive fibers changes significantly with the movement of the wrist joint, proving that it can be used to monitor the wrist joint movement.

[0037] Example 3

[0038] (1) 7 g of wheat gluten was taken and added to a mixed solution composed of 28 mL of 6 mmol / L tri-aldehyde m-benzene triol n-octanoic acid solution and 35 mL of hexafluoroisopropanol, and stirred at 40°C for 3 h to form a protein solution;

[0039] (2) After the protein solution was vacuum degassed, dry-wet spinning was carried out under the conditions of a pressure of 0.6 MPa and a temperature of 50°C using a coaxial spinneret (with ethanol as a coagulation bath for solidification and molding) to form a hollow protein wet fiber;

[0040] (3) The spun hollow protein wet fiber is sequentially washed with ethanol, washed with water, and vacuum dried at room temperature, 4 g of the hollow protein fiber is placed in 160 mL of a 2,5-diamino-1,4-benzenedisulfonic acid solution with a concentration of 5 mmol / L, and in-situ covalent organic framework is generated on the surface and inner wall of the hollow protein fiber by reacting at 55 °C for 90 h in an air-tight manner, and then the protein hollow conductive fiber is obtained by washing with water and vacuum drying after the covalent organic framework is generated.

[0041] A bundle of the protein hollow conductive fibers is adhered to the knee, and the relative resistance change is tested along with the movement of the knee joint, and the result is shown in Figure 3 It can be known from Figure 3 that the relative resistance value of the conductive fiber composed of the protein hollow conductive fiber changes significantly along with the movement of the knee joint, which proves that the conductive fiber can be used to monitor the movement of the knee joint.

[0042] Comparative Example 1

[0043] (1) 6 g of keratin is added to 60 mL of a hexafluoroisopropanol solution, and the reaction is stirred at 50 °C for 1 h to form a protein solution;

[0044] (2) After the protein solution is vacuum degassed, the dry-wet spinning is performed under the conditions of a pressure of 0.6 MPa and a temperature of 50 °C by using a coaxial spinneret (ethanol is used as a coagulation bath for solidification and molding) to form a hollow protein wet fiber;

[0045] (3) 30 mL of a 5 mmol / L tri-aldehyde phloroglucinol n-octanoic acid solution is mixed with 150 mL of a 2,5-diamino-1,4-benzenedisulfonic acid solution with a concentration of 4 mmol / L, and in-situ covalent organic framework is generated on the surface and inner wall of the hollow protein fiber by reacting at 60 °C for 80 h in an air-tight manner, and then the protein hollow conductive fiber is obtained by washing with water and vacuum drying after the covalent organic framework is generated.

[0046] (4) After the spun hollow protein wet fiber is sequentially washed with ethanol, washed with water, and vacuum dried at room temperature, 3 g of the hollow protein fiber is placed in 150 mL of the covalent organic framework solution for 12 h of impregnation, and then the protein hollow conductive fiber is obtained by washing with water and vacuum drying.

[0047] Comparative Example 2

[0048] (1) 6 g of keratin is added to a mixed solution composed of 30 mL of a 5 mmol / L tri-aldehyde phloroglucinol n-octanoic acid solution and 30 mL of hexafluoroisopropanol, and the reaction is stirred at 50 °C for 1 h to form a protein solution;

[0049] (2) After the protein solution is vacuum degassed, the dry-wet spinning is performed under the conditions of a pressure of 0.6 MPa and a temperature of 50 °C by using a coaxial spinneret (ethanol is used as a coagulation bath for solidification and molding) to form a hollow protein wet fiber;

[0050] (3) the spun protein fiber is sequentially washed by ethanol, washed by water, vacuum dried at room temperature, 3g of the protein fiber is placed in 150mL of 2,5-diamino-1,4-benzenedisulfonic acid solution with a concentration of 4mmol / L, and the reaction is carried out at 60℃ for 80h in an air-tight manner, and then the protein conductive fiber is obtained by washing by water and vacuum drying.

[0051] The properties of the protein conductive fibers prepared in each example and the comparative example are tested, and the results are shown in Table 1.

[0052] Table 1: Property test of different protein conductive fibers

[0053]

[0054] As shown in Table 1, the conductivity of the protein hollow conductive fiber obtained in the example can reach more than 7S / m, indicating that it has good conductive performance. This is mainly because the surface and the inner wall of the hollow cavity of the protein hollow fiber are loaded with covalent organic frameworks, which generates ion transmission channels and gives the protein hollow fiber a high ionic conductivity. Compared with the example, the protein hollow conductive fiber formed by directly compounding the protein hollow fiber with the covalent organic framework in the comparative example 1 has a conductivity much lower than that of the example. This may be because the covalent organic framework is a two-dimensional nanomaterial, which is prone to aggregation and forms covalent organic framework powder. The boundaries between randomly oriented lamellae in the covalent organic framework powder hinder the ion transfer. The conductivity of the protein conductive fiber in the comparative example 2 is also greatly reduced compared with the example. This is because the specific cavity structure of the directional arrangement of the protein hollow fiber is lacking, the covalent organic framework cannot be confined to grow, and the highly ordered ion transfer channel cannot be formed, resulting in random orientation of the one-dimensional ion channel in the covalent organic framework, which greatly affects the transfer efficiency of the ions.

[0055] The above only describes the preferred embodiments of the present application, and any equivalent changes and modifications made within the scope of the present application should be included in the scope of the present application.

Claims

1. A method of making a protein hollow conductive fiber, characterized by: The method comprises the following steps: (1) uniformly mixing a n-octanoic acid solution of tri-aldehyde-based phloroglucinol with hexafluoroisopropanol, adding a protein, and then reacting at 25-50 DEG C for 1-5 h to form a protein solution; (2) vacuum degassing the protein solution obtained in step (1) and then spinning to form a hollow protein wet fiber; (3) sequentially washing the hollow protein wet fiber spun in step (2) with ethanol, water, and vacuum drying at room temperature, then placing it in a 2,5-diamino-1,4-benzenedisulfonic acid solution, and reacting in an air-tight manner for a certain period of time to in-situ form a covalent organic framework on the surface of the hollow protein fiber and the inner wall of the cavity, and then washing with water and vacuum drying to form the protein hollow conductive fiber; In step (3), the reaction temperature is 50-60 DEG C, and the reaction time is 80-100 h.

2. The method for preparing a protein hollow conductive fiber according to claim 1, characterized in that: In step (1), the protein is any one of keratin, collagen, and gluten.

3. The method for preparing a protein hollow conductive fiber according to claim 1, characterized in that: In step (1), the use amount ratio of the protein to the n-octanoic acid solution of tri-aldehyde-based phloroglucinol and hexafluoroisopropanol is 2 g:5-10 mL:10 mL; and the concentration of the n-octanoic acid solution of tri-aldehyde-based phloroglucinol is 5-7.5 mmol / L.

4. The method for preparing a protein hollow conductive fiber according to claim 1, characterized in that: In step (2), the hollow protein wet fiber is specifically prepared by dry-wet spinning of the protein solution under the conditions of a pressure of 0.6 MPa and a temperature of 50 DEG C using a coaxial spinneret.

5. The method for preparing a protein hollow conductive fiber according to claim 1, characterized in that: In step (3), the use amount ratio of the hollow protein wet fiber to the 2,5-diamino-1,4-benzenedisulfonic acid solution is 1 g:25-50 mL; and the concentration of the 2,5-diamino-1,4-benzenedisulfonic acid solution is 4-6 mmol / L.

6. A protein hollow conductive fiber prepared by any one of the methods in claims 1-5.

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