Regenerated filament with high mechanical property and preparation method thereof

Abstract

The invention relates to a regenerated filament with high mechanical property and a preparation method thereof. The method comprises the following steps: (1) preparing materials: preparing a chromium carbide (Cr3C2) suspension; and (2) preparation of functional regenerated silk (RSF): mixing the Cr3C2 suspension with the silk fibroin solution, and preparing a functional Cr3C2 / RSF fiber compound by a wet spinning method. Cr3C2 obviously enhances the mechanical property of the RSF and the absorption effect of the RSF on ultraviolet light, and shows the excellent anti-ultraviolet property of the RSF. When Cr3C2 is not doped, the breaking strength of the RSF fiber is 203.32 + / -5.22 MPa, and the breaking strength is enhanced to 313.23 + / -3.68 MPa after the RSF fiber is doped. After ultraviolet aging treatment, the breaking strength of the RSF fiber is reduced to 126.54 + / -4.88 MPa, and the breaking strength of Cr3C2 / RSF is 263.42 + / -4.30 MPa. The composite fiber has good stability and biological safety, and has good application potential in the fields of biomedicine and functional textile.

Description

Technical Field

[0001] The present invention belongs to the field of modification of silk, and more specifically, relates to a regenerated silk with high mechanical properties and a preparation method thereof. Background Art

[0002] Regenerated silk fibroin (RSF) fiber is a natural high-performance biomaterial with good biocompatibility, mechanical properties, environmental friendliness and degradability, and has broad application potential in the fields of functional textiles, biomedical dressings and flexible electronics. However, natural and RSF face many challenges in practical applications. For example, it is prone to aging and a decrease in mechanical properties under the irradiation of ultraviolet light, high temperature and sweat environments, which seriously affects its extended application in the field of fiber materials. Therefore, how to improve its ultraviolet adaptability and functionality without destroying the silk protein structure has become the key to the functionalization research of RSF materials. Summary of the Invention

[0003] Object of the Invention: The object of the present invention is to provide a preparation method of a regenerated silk with high mechanical properties that significantly improves ultraviolet resistance; another object of the present invention is to provide a regenerated silk with high mechanical properties.

[0004] Technical Solution: A preparation method of a regenerated silk with high mechanical properties according to the present invention includes the following steps:

[0005] (1) Prepare a chromium carbide (Cr 3 C 2 ) suspension;

[0006] (2) Prepare a functional regenerated silk (RSF) fiber: Mix the Cr 3 C 2 suspension with a silk fibroin solution to obtain a Cr 3 C 2 / RSF mixed solution, and prepare the Cr 3 C 2 / RSF mixed solution into a functional Cr 3 C 2 / RSF fiber composite, that is, a regenerated silk with high mechanical properties, by the wet spinning method.

[0007] Further, in step (1), the size of the used Cr 3 C 2 is 480 nm - 520 nm.

[0008] Further, in step (2), the preparation method of the silk fibroin solution is: Dissolve degummed silk in a formic acid solution of calcium chloride, stir, and disperse evenly to obtain a silk fibroin solution.

[0009] Furthermore, the mass concentration of calcium chloride is 5%-10%, and the mass concentration of the prepared silk fibroin solution is 10%-15%.

[0010] Preferably, the mass concentration of calcium chloride is 5%, and the mass concentration of the prepared silk fibroin solution is 15%.

[0011] Furthermore, in step (2), Cr 3 C 2 In the / RSF mixed solution, the mass ratio of Cr 3 C 2 to RSF is 1-5:100.

[0012] Preferably, in the preparation of the Cr 3 C 2 / RSF fiber composite, the mass ratio of Cr 3 C 2 to regenerated silk (RSF) is 1:100, 2:100, 3:100, 4:100, 5:100.

[0013] Furthermore, in step (2), the wet spinning method is as follows: Inject the Cr 3 C 2 / RSF mixed solution into the coagulation bath, and use ethanol as the coagulating liquid; the Cr 3 C 2 / RSF mixed solution enters the coagulation bath through the spinning needle, and then quickly coagulates into a uniform filamentous Cr 3 C 2 / RSF fiber in the coagulation bath, and is wound on the rotating shaft for collection after stretching treatment.

[0014] Furthermore, in the wet spinning method, 75% ethanol is used as the coagulating liquid.

[0015] Furthermore, in the wet spinning method, the Cr 3 C 2 / RSF mixed solution enters the coagulation bath through the spinning needle at a speed of 33.33 μL / min.

[0016] Furthermore, the collected Cr 3 C 2 / RSF fiber is placed in a 75% ethanol solution to remove the residual solvent and shape it, and then air-dried naturally.

[0017] As a preferred embodiment, the wet spinning method is as follows: Inject the Cr 3 C 2The CDs / RSF mixed solution was injected into a coagulation bath with a length of 1 m. 75% ethanol was used as the coagulating liquid, and it entered the coagulation bath through a spinning needle at a speed of 33.33 μL / min. The mixed solution quickly coagulated into uniform filamentous fibers in the coagulation bath, and after stretching treatment, it was wound around a rotating shaft for collection.

[0018] On the other hand, the present invention provides a regenerated silk with high mechanical properties prepared by the above method.

[0019] Beneficial effects: The present invention has the following remarkable advantages: without doping Cr 3 C 2 When not doped, the breaking strength of the RSF fiber is 203.32 ± 5.22 MPa. After doping, the breaking strength is enhanced to 313.23 ± 3.68 MPa, which is 1.54 times that of the original. After ultraviolet aging treatment, the breaking strength of the RSF fiber drops to 126.54 ± 4.88 MPa, while that of Cr 3 C 2 / RSF is 263.42 ± 4.30 MPa, which is 2.08 times that of the original. Description of the drawings

[0020] Figure 1 Tensile test diagrams of the Cr 3 C 2 / RSF silk fibers obtained in Examples 1 - 5;

[0021] Figure 2 Tensile test diagrams of the Cr 3 C 2 / RSF silk fibers after ultraviolet aging in Example 6;

[0022] Figure 3 Tensile test diagrams of the silk fibers obtained in Comparative Examples 1 and 2 before and after ultraviolet aging. Detailed implementation manners

[0023] The technical solution of the present invention will be further described below in conjunction with the drawings.

[0024] The chromium carbide used in the examples of the present invention was purchased from: Hebei Yuanying New Materials Co., Ltd., with a specification of 500 nm.

[0025] Example 1

[0026] This example provides a preparation method for a regenerated silk with high mechanical properties, including the following steps:

[0027] Accurately weigh 1.0 g of anhydrous calcium chloride (CaCl 2 ) and 19.0 g of formic acid (FA) solution, mix them and stir until dissolved to prepare a 5 wt% FA - CaCl 2The solution was refrigerated at 4 °C for later use. Weighed 0.5 g of degummed silk fibroin and dissolved it in 2.835 g of FA-CaCl 2 solution, and stirred for 4 h at room temperature to prepare a 15 wt% RSF solution.

[0028] Mix Cr 3 C 2 with the silk fibroin solution, and prepare a functional Cr 3 C 2 / RSF fiber composite by wet spinning method: First, add Cr 3 C 2 to a formic acid solution containing 5 wt% calcium chloride and stir for 0.5 h to make Cr 3 C 2 uniformly dispersed in the solution to obtain a Cr 3 C 2 suspension. Add 0.5 g of degummed silk fibroin and stir for 4 h to prepare a 1 wt% Cr 3 C 2 / RSF solution (the mass ratio of Cr 3 C 2 to RSF is 1:100).

[0029] Using a self-made wet spinning device, inject the spinning dope into the coagulation bath through a syringe. The length of the coagulation bath is 1 m, and 75% ethanol is used as the coagulation liquid. The spinning dope enters the coagulation bath through the spinneret at a speed of 33.33 μL / min. The spinning dope quickly coagulates into uniform filamentous fibers in the coagulation bath. The as-spun fibers are collected on the rotating shaft after stretching treatment. The collected RSF fibers are placed in a 75% ethanol solution for 2 hours to remove the residual solvent and be shaped. Finally, the RSF fibers are taken out and air-dried for 24 hours.

[0030] The breaking strength of the Cr 3 C 2 / RSF fibers obtained in Example 1 was concentrated at 261.54 ± 3.61 MPa ( Figure 1 ).

[0031] Example 2

[0032] The specific implementation method is basically the same as that of Example 1, except that the mass ratio of Cr 3 C 2 to RSF is 2:100.

[0033] The breaking strength of the CDs / RSF fibers obtained in Example 2 was concentrated at 266.88 ± 4.64 MPa ( Figure 1 ).

[0034] Example 3

[0035] The specific implementation method is basically the same as that of Example 1, except that the mass ratio of Cr 3 C 2 to RSF is 3:100.

[0036] The breaking strength of the Cr 3 C 2 / RSF fibers obtained in Example 3 is concentrated at 313.23 ± 3.68 MPa( Figure 1 ).

[0037] Example 4

[0038] The specific implementation method is basically the same as that of Example 1, except that the mass ratio of Cr 3 C 2 to RSF is 4:100.

[0039] The breaking strength of the Cr 3 C 2 / RSF fibers obtained in Example 4 is concentrated at 296.83 ± 6.81 MPa( Figure 1 ).

[0040] Example 5

[0041] The specific implementation method is basically the same as that of Example 1, except that the mass ratio of Cr 3 C 2 to RSF is 5:100.

[0042] The breaking strength of the CDs / RSF fibers obtained in Example 5 is concentrated at 286.50 ± 3.50 MPa( Figure 1 ).

[0043] Example 6

[0044] After obtaining the Cr 3 C 2 / RSF fibers in Example 3, they were placed outdoors under natural light for 30 days (RH: 70%, 26 °C). After the aging was completed, the samples were taken out and placed in a disposable plastic bag and stored at room temperature in the dark for tensile property testing. The results are as Figure 2 shown, the breaking strength of the Cr 3 C 2 / RSF fibers is concentrated at 263.42 ± 4.30 MPa.

[0045] Comparative Example 1

[0046] The specific implementation method is basically the same as that of Example 1, except that in step (1), the added Cr 3 C 2It is 0 g. This comparative example is a blank control group. The breaking strength of the obtained RSF was tested according to the method in Example 1, and the results are as Figure 3 shown. The breaking strength of the silk fiber is concentrated at 203.32 ± 5.22 MPa.

[0047] Comparative Example 2

[0048] The specific implementation method is basically the same as that of Example 6, except that the fiber tested is not Cr 3 C 2 / RSF, but the blank control RSF fiber. The results are as Figure 3 shown. The breaking strength of the RSF fiber is concentrated at 126.54 ± 4.88 MPa.

Claims

1. A method for preparing regenerated silk with high mechanical properties, characterized in that: The steps include: (1) preparing a Cr3C2 suspension; (2) Preparation of functional regenerated silk fibers: Mixing a Cr3C2 suspension with a silk fibroin solution to obtain a Cr3C2 / RSF mixed solution, and preparing the Cr3C2 / RSF mixed solution into a functional Cr3C2 / RSF fiber composite, i.e., regenerated silk with high mechanical properties, by a wet spinning method.

2. The method for preparing regenerated silk with high mechanical properties according to claim 1, characterized in that: In step (1), the size of Cr3C2 used is 480nm-520nm.

3. The method for preparing regenerated silk with high mechanical properties according to claim 1, characterized in that: In step (2), the preparation method of the silk fibroin solution is: dissolving the degummed silk in a formic acid solution of calcium chloride, stirring, and dispersing uniformly to obtain the silk fibroin solution.

4. The method for preparing regenerated silk with high mechanical properties according to claim 3, characterized in that: The mass concentration of calcium chloride is 5%-10%, and the mass concentration of the prepared silk fibroin solution is 10%-15%.

5. The method for preparing regenerated silk with high mechanical properties according to claim 1, characterized in that: In step (2), in the Cr3C2 / RSF mixed solution, the mass ratio of Cr3C2 to RSF is 1-5:

100.

6. The method for preparing regenerated silk with high mechanical properties according to claim 1, characterized in that: In step (2), the wet spinning method is as follows: injecting the Cr3C2 / RSF mixed solution into a coagulation tank, using ethanol as the coagulation liquid; the Cr3C2 / RSF mixed solution enters the coagulation bath through a spinning needle, and then rapidly coagulates into uniform filamentous Cr3C2 / RSF fibers in the coagulation bath, which are then wound on a rotating shaft and collected after being stretched.

7. The method for preparing regenerated silk with high mechanical properties according to claim 6, characterized in that: In the wet spinning method, 75% ethanol is used as the coagulation liquid.

8. The method for preparing regenerated silk with high mechanical properties according to claim 6, characterized in that: In the wet spinning method, the Cr3C2 / RSF mixed solution enters the coagulation bath through the spinning needle at a speed of 33.33 μL / min.

9. The method for preparing regenerated silk with high mechanical properties according to claim 6, characterized in that: The collected Cr3C2 / RSF fibers were placed in a 75% ethanol solution to remove the residual solvent and fix the shape, and then air-dried naturally.

10. A regenerated yarn with high mechanical properties prepared by the method according to any one of claims 1 to 9.

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