Method for producing spider protein fiber by utilizing spider protein

Abstract

The invention relates to the technical field of spider protein fibers, and provides a method for producing spider protein fibers by using spider protein, which comprises the following steps: spinning a spinning solution to obtain spider protein fibers; the spinning solution is prepared from the following components in parts by weight: 20 to 30 parts of spider silk protein, 5 to 6 parts of sodium hydroxide, 4 to 10 parts of methyl tetrahydrophthalic anhydride, 1 to 11 parts of 1-allyl-3-ethylimidazolium bromide, 1 to 3 parts of glutaraldehyde and 100 parts of solvent. According to the technical scheme, the problem that the mechanical property of the spider protein fiber is poor in the prior art is solved.

Description

Technical Field

[0001] The present invention relates to the technical field of spider protein fibers, and in particular to a method for producing spider protein fibers by utilizing spider proteins. Background Art

[0002] Spider protein fiber, also known as spider silk fiber or spider silk fiber, is a polymer fiber composed of spider protein. This fiber has a unique molecular structure, specifically composed of β-folds composed of alanine and A-helices rich in proline tightly stacked together, forming a semi-crystalline molecular spring structure. It is this structure that gives spider protein fiber a series of excellent properties, such as good elasticity, light weight and biodegradability, making it have a wide range of application potential in many fields such as textiles, military, aerospace, and medicine.

[0003] Although spider protein fibers have certain mechanical properties, they still have problems with insufficient and unstable mechanical properties, which to a certain extent limit their application in fields requiring higher mechanical properties. These mechanical defects have become a bottleneck restricting the application and development of spider protein fibers in a wider range of fields. Therefore, proposing a method that can effectively utilize spider protein to produce spider protein fibers with excellent mechanical properties is of vital importance to further expand the scope of application of spider protein fibers. Summary of the invention

[0004] The present invention provides a method for producing spider protein fibers using spider protein, which solves the problem of poor mechanical properties of spider protein fibers in the related art.

[0005] The technical solution of the present invention is as follows: The present invention provides a method for producing spider protein fibers using spider protein, comprising the following steps: spinning a spinning solution to obtain spider protein fibers; The spinning solution comprises the following components in parts by weight: 20-30 parts of spider silk protein, 5-6 parts of sodium hydroxide, 4-10 parts of methyltetrahydrophthalic anhydride, 1-11 parts of 1-allyl-3-ethylimidazolium bromide, 1-3 parts of glutaraldehyde, and 100 parts of solvent.

[0006] As a further technical solution, the weight ratio of the methyltetrahydrophthalic anhydride to the 1-allyl-3-ethylimidazolium bromide is 1-3:1.

[0007] When the weight ratio of methyltetrahydrophthalic anhydride to 1-allyl-3-ethylimidazolium bromide is 1-3:1, the mechanical properties of spider protein fibers can be further improved.

[0008] As a further technical solution, the spinning solution also includes 5 to 10 parts of mesoporous carbon.

[0009] In the present invention, mesoporous carbon is introduced into the spinning solution. After the spider protein fiber is prepared, the mesoporous carbon can be filled in the internal structure of the spider protein fiber through the effective combination of the mesoporous carbon and the components in the spinning solution. The internal structure stability of the spider protein fiber can be further improved, thereby further improving the mechanical properties of the spider protein fiber.

[0010] As a further technical solution, the mesoporous carbon is modified mesoporous carbon; the raw materials of the modified mesoporous carbon include mesoporous carbon and polyetherimide.

[0011] By using polyetherimide to modify the surface of mesoporous carbon, the mesoporous carbon can be dispersed more evenly in the spinning solution, and its binding effect with the components in the spinning solution can be further enhanced, thereby further improving the mechanical properties of spider protein fibers.

[0012] As a further technical solution, the weight ratio of the mesoporous carbon to the polyetherimide is 4-9:1.

[0013] When the weight ratio of mesoporous carbon to polyetherimide is 4~9:1, the mechanical properties of spider protein fibers can be further improved.

[0014] As a further technical solution, the preparation method of the modified mesoporous carbon comprises the following steps: dispersing the mesoporous carbon evenly in dimethylformamide, adding the polyetherimide, stirring, and drying to obtain the modified mesoporous carbon.

[0015] As a further technical solution, the raw material of the modified mesoporous carbon also includes isobutylamide.

[0016] When the raw materials for modifying mesoporous carbon also include isobutylamide, the mechanical properties of spider protein fibers can be further improved by modifying the mesoporous carbon with isobutylamide and polyetherimide. The reason may be that the presence of isobutylamide can make the mesoporous carbon and polyetherimide more closely combined, while enhancing its modification effect, it can further enhance the combination of mesoporous carbon and other components, thereby further improving the mechanical properties of spider protein fibers.

[0017] As a further technical solution, the weight ratio of the mesoporous carbon, the polyetherimide and the isobutyramide is 18:2:1-2.

[0018] When the weight ratio of mesoporous carbon, polyetherimide and isobutyramide is 18:2:1~2, the mechanical properties of spider protein fibers can be further improved.

[0019] As a further technical solution, the preparation method of the modified mesoporous carbon includes the following steps: dispersing the mesoporous carbon evenly in dimethylformamide, adding the polyetherimide and the isobutylamide, stirring, and drying to obtain the modified mesoporous carbon.

[0020] As a further technical solution, the solvent is water and an organic solvent, and the organic solvent includes one of ethanol, acetone, and isopropanol.

[0021] As a further technical solution, the volume ratio of water to organic solvent is 4:1.

[0022] As a further technical solution, the preparation of the spinning solution comprises the following steps: S1, dispersing spider silk protein in a solvent and stirring to obtain a protein solution; S2. Add the remaining components to the protein solution, mix evenly, and stir to obtain a spinning solution.

[0023] As a further technical solution, the spinning specifically comprises the following steps: A1, filtering the spinning solution, vacuum degassing, spinning, and coagulating in a coagulation liquid to form primary fibers; A2. Dry-heat stretching, water washing and drying the nascent fibers to obtain spider protein fibers.

[0024] As a further technical solution, in step S1, the stirring temperature is 50-60°C and the stirring time is 1-2h; in step S2, the stirring temperature is 80-90°C and the stirring time is 4-5h.

[0025] As a further technical solution, in step A1, during the spinning, the aperture of the spinneret is 1.3-1.8 mm.

[0026] As a further technical solution, in step A1, the volume ratio of the spinning solution to the coagulation solution is 1:2-3, and the coagulation solution comprises dimethylformamide and water in a volume ratio of 3:2; during the coagulation, the temperature is 10-14°C.

[0027] As a further technical solution, in step A2, during the dry heat stretching, the temperature is 150-180°C and the stretching ratio is 2.6-3.0 times.

[0028] As a further technical solution, the method for preparing the spider silk protein comprises the following steps: B1, taking natural spider silk and 0.5wt% sodium hydroxide solution at a mass volume ratio of 1g:20mL, boiling, and stirring until the solution is colorless and transparent to obtain the treated spider silk; B2, freezing the treated spider silk at -25°C for 2 hours, and freeze-drying for 36 hours to obtain purified spider silk; B3. Mix the purified spider silk with hexafluoroisopropanol in a mass volume ratio of 3 g:20 mL, stir, and centrifuge to obtain a supernatant. After filtering the supernatant, drop it into anhydrous ethanol for precipitation to obtain spider silk protein; the volume ratio of the supernatant to the anhydrous ethanol is 1:3.

[0029] The working principle and beneficial effects of the present invention are: In the present invention, after spider silk protein is combined with other components to form a spinning solution, the spider protein fiber produced by spinning has high mechanical properties. Among them, the spinning solution includes methyltetrahydrophthalic anhydride and 1-allyl-3-ethylimidazolium bromide. Through the combined use of methyltetrahydrophthalic anhydride and 1-allyl-3-ethylimidazolium bromide and the spider silk protein, the spider silk protein can have a high solubility in the solution system and enhance the overall stability of the protein solution, so that the spider protein fiber produced has a stable internal structure, thereby significantly improving its mechanical properties. DETAILED DESCRIPTION

[0030] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] In the following examples and comparative examples, spider silk protein is prepared from natural spider silk, and the natural spider silk is the silk of the spider spider of the taenia jingzhao; the model of the mesoporous carbon is Brofos-JC-W800, with an average particle size of 800 μm and a pore size of 8.5 nm; and the model of the polyetherimide is DU319-1000.

[0032] Example 1 A method for producing spider protein fibers using spider protein comprises the following steps: a spinning solution is spun to obtain spider protein fibers, wherein the spinning solution comprises the following components in parts by weight: 20 parts of spider silk protein, 5 parts of sodium hydroxide, 4 parts of methyltetrahydrophthalic anhydride, 1 part of 1-allyl-3-ethylimidazolium bromide, 1 part of glutaraldehyde, and 100 parts of solvent; The solvent was water and ethanol in a volume ratio of 4:1; The preparation of the spinning solution comprises the following steps: S1, dispersing spider silk protein in a solvent, stirring at 50°C for 2h to obtain a protein solution; S2. Add the remaining components to the protein solution, mix well, and stir at 80° C. for 5 h to obtain a spinning solution; Spinning specifically includes the following steps: A1. Filter the spinning solution, vacuum degas, spin under a spinneret with a pore size of 1.3 mm, and coagulate in a coagulation solution formed by dimethylformamide and water in a volume ratio of 3:2 (the volume ratio of the spinning solution to the coagulation solution is 1:2), and the coagulation temperature is 12°C to form primary fibers; A2. Dry-heat stretching the spun fibers at 150° C. to 2.6 times the length of the spun fibers, and then washing and drying the fibers to obtain spider protein fibers.

[0033] Example 2 A method for producing spider protein fibers using spider protein comprises the following steps: a spinning solution is spun to obtain spider protein fibers, wherein the spinning solution comprises the following components in parts by weight: 25 parts of spider silk protein, 5.5 parts of sodium hydroxide, 5 parts of methyltetrahydrophthalic anhydride, 7 parts of 1-allyl-3-ethylimidazolium bromide, 2 parts of glutaraldehyde, and 100 parts of solvent; The solvent was water and ethanol in a volume ratio of 4:1; The preparation of the spinning solution comprises the following steps: S1, dispersing spider silk protein in a solvent, stirring at 55°C for 1.5h to obtain a protein solution; S2. Add the remaining components to the protein solution, mix well, and stir at 85° C. for 4.5 h to obtain a spinning solution; Spinning specifically includes the following steps: A1. Filter the spinning solution, vacuum degas, spin under a spinneret with a pore size of 1.5 mm, and coagulate in a coagulation solution formed by dimethylformamide and water in a volume ratio of 3:2 (the volume ratio of the spinning solution to the coagulation solution is 1:3), and the coagulation temperature is 12°C to form primary fibers; A2. Dry-heat stretching the spun fibers at 165° C. to 2.8 times the length of the spun fibers, and then washing and drying the fibers to obtain spider protein fibers.

[0034] Example 3 A method for producing spider protein fibers using spider protein comprises the following steps: a spinning solution is spun to obtain spider protein fibers, wherein the spinning solution comprises the following components in parts by weight: 30 parts of spider silk protein, 6 parts of sodium hydroxide, 10 parts of methyltetrahydrophthalic anhydride, 11 parts of 1-allyl-3-ethylimidazolium bromide, 3 parts of glutaraldehyde, and 100 parts of solvent; The solvent was water and ethanol in a volume ratio of 4:1; The preparation of the spinning solution comprises the following steps: S1, dispersing spider silk protein in a solvent, stirring at 60°C for 1 hour to obtain a protein solution; S2. Add the remaining components to the protein solution, mix well, and stir at 90° C. for 4 hours to obtain a spinning solution; Spinning specifically includes the following steps: A1. Filter the spinning solution, vacuum degas, spin under a spinneret with a pore size of 1.8 mm, and coagulate in a coagulation solution formed by dimethylformamide and water in a volume ratio of 3:2 (the volume ratio of the spinning solution to the coagulation solution is 1:3), and the coagulation temperature is 12°C to form primary fibers; A2. Dry-heat stretching the spun fibers at 165° C. to 3.0 times the length of the spun fibers, and then washing and drying the fibers to obtain spider protein fibers.

[0035] Example 4 The only difference between this embodiment and embodiment 2 is that in this embodiment, 10 parts of methyltetrahydrophthalic anhydride and 2 parts of 1-allyl-3-ethylimidazolium bromide are added to the spinning solution.

[0036] Example 5 The only difference between this embodiment and embodiment 2 is that in this embodiment, 6 parts of methyltetrahydrophthalic anhydride and 6 parts of 1-allyl-3-ethylimidazolium bromide are added to the spinning solution.

[0037] Example 6 The only difference between this embodiment and embodiment 2 is that in this embodiment, 9 parts of methyltetrahydrophthalic anhydride and 3 parts of 1-allyl-3-ethylimidazolium bromide are added to the spinning solution.

[0038] Example 7 The only difference between this embodiment and embodiment 6 is that in this embodiment, the spinning solution further includes 5 parts of mesoporous carbon.

[0039] Example 8 The only difference between this embodiment and embodiment 6 is that in this embodiment, the spinning solution further includes 10 parts of mesoporous carbon.

[0040] Example 9 The only difference between this embodiment and Embodiment 8 is that in this embodiment, the mesoporous carbon is modified mesoporous carbon, and its preparation method includes the following steps: dispersing 7.5 parts of mesoporous carbon evenly in 15 parts of dimethylformamide, adding 2.5 parts of polyetherimide, stirring, and drying to obtain modified mesoporous carbon.

[0041] Example 10 The only difference between this embodiment and embodiment 9 is that in this embodiment, 9.5 parts of mesoporous carbon and 0.5 parts of polyetherimide are added.

[0042] Embodiment 11 The only difference between this embodiment and embodiment 9 is that in this embodiment, 9 parts of mesoporous carbon and 1 part of polyetherimide are added.

[0043] Example 12 The only difference between this embodiment and embodiment 9 is that in this embodiment, 8 parts of mesoporous carbon and 2 parts of polyetherimide are added.

[0044] Embodiment 13 The only difference between this embodiment and Embodiment 11 is that in this embodiment, the mesoporous carbon is modified mesoporous carbon, and its preparation method includes the following steps: dispersing 18 parts of mesoporous carbon evenly in 15 parts of dimethylformamide, adding 2 parts of polyetherimide and 0.5 parts of isobutylamide, stirring, concentrating to dryness, and obtaining modified mesoporous carbon.

[0045] Embodiment 14 The only difference between this embodiment and embodiment 13 is that in this embodiment, 18 parts of mesoporous carbon, 2 parts of polyetherimide and 2.5 parts of isobutyramide are added.

[0046] Embodiment 15 The only difference between this embodiment and embodiment 13 is that in this embodiment, 18 parts of mesoporous carbon, 2 parts of polyetherimide and 1 part of isobutylamide are added.

[0047] Example 16 The only difference between this embodiment and embodiment 13 is that in this embodiment, 18 parts of mesoporous carbon, 2 parts of polyetherimide and 2 parts of isobutylamide are added.

[0048] Comparative Example 1 The difference between this comparative example and Example 1 is that in this comparative example, no methyltetrahydrophthalic anhydride is added to the spinning solution, and 5 parts of 1-allyl-3-ethylimidazolium bromide are added.

[0049] Comparative Example 2 The difference between this comparative example and Example 1 is that in this comparative example, no 1-allyl-3-ethylimidazolium bromide is added to the spinning solution, and 5 parts of methyltetrahydrophthalic anhydride are added.

[0050] Comparative Example 3 The difference between this comparative example and Example 1 is that in this comparative example, neither methyltetrahydrophthalic anhydride nor 1-allyl-3-ethylimidazolium bromide is added to the spinning solution.

[0051] Experimental example Mechanical properties test The breaking strength and breaking elongation of the spider protein fibers prepared in Examples 1 to 16 and Comparative Examples 1 to 3 were tested using an electronic single fiber strength tester (model: YG003A), wherein the stretching speed was 5 mm / min. The test results are shown in Table 1 below: Table 1 Mechanical properties test results of Examples 1 to 16 and Comparative Examples 1 to 3

[0052] Compared with comparative examples 1 to 3, the breaking strength and breaking elongation of Example 1 are significantly improved, indicating that the spinning solution includes methyltetrahydrophthalic anhydride and 1-allyl-3-ethylimidazolium bromide, and the two have a synergistic effect. By using the two together, the prepared spider protein fiber can have a stable internal structure, thereby improving the mechanical properties of the spider protein fiber.

[0053] Compared with Examples 2 and 4, the breaking strength and breaking elongation of Examples 5 to 6 are improved, indicating that when the weight ratio of methyltetrahydrophthalic anhydride to 1-allyl-3-ethylimidazolium bromide is 1 to 3:1, the mechanical properties of spider protein fibers can be further improved.

[0054] Compared with Example 6, the breaking strength and breaking elongation of Examples 7 to 8 are improved, indicating that when mesoporous carbon is introduced into the spinning solution, the mechanical properties of the spider protein fiber are further improved through the effective combination of the mesoporous carbon and the components in the spinning solution.

[0055] Compared with Example 8, the breaking strength and elongation at break of Examples 9 to 12 are improved, indicating that the mechanical properties of spider protein fibers can be further improved by surface modification of mesoporous carbon using polyetherimide. Compared with Examples 9 to 10, the breaking strength and elongation at break of Examples 11 to 12 are improved, indicating that when the weight ratio of mesoporous carbon to polyetherimide is 4 to 9:1, the mechanical properties of spider protein fibers can be further improved.

[0056] Compared with Example 11, the breaking strength and elongation at break of Examples 13 to 16 are improved, indicating that when the raw material for modifying the mesoporous carbon also includes isobutylamide, the mechanical properties of the spider protein fiber can be further improved by modifying the mesoporous carbon with isobutylamide and polyetherimide. Compared with Examples 13 to 14, the breaking strength and elongation at break of Examples 15 to 16 are improved, indicating that when the weight ratio of mesoporous carbon, polyetherimide and isobutylamide is 18:2:1 to 2, the mechanical properties of the spider protein fiber can be further improved.

[0057] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for producing spider protein fiber using spider protein, characterized in that: The following steps are involved: After spinning the spinning solution, spider protein fibers are obtained; The spinning solution comprises the following components in parts by weight: 20-30 parts of spider silk protein, 5-6 parts of sodium hydroxide, 4-10 parts of methyltetrahydrophthalic anhydride, 1-11 parts of 1-allyl-3-ethylimidazolium bromide, 1-3 parts of glutaraldehyde, and 100 parts of solvent.

2. A method for producing spider protein fiber using spider protein according to claim 1, characterized in that: The weight ratio of the methyltetrahydrophthalic anhydride to the 1-allyl-3-ethylimidazolium bromide is 1-3:

1.

3. The method for producing spider protein fiber using spider protein according to claim 1, characterized in that: The spinning solution also includes 5 to 10 parts of mesoporous carbon.

4. A method for producing spider protein fiber using spider protein according to claim 3, characterized in that: The mesoporous carbon is modified mesoporous carbon; the raw materials of the modified mesoporous carbon include mesoporous carbon and polyetherimide.

5. The method for producing spider protein fiber using spider protein according to claim 4, characterized in that: The weight ratio of the mesoporous carbon to the polyetherimide is 4-9:

1.

6. The method for producing spider protein fiber using spider protein according to claim 4, characterized in that: The preparation method of the modified mesoporous carbon comprises the following steps: dispersing the mesoporous carbon evenly in dimethylformamide, adding the polyetherimide, stirring, and drying to obtain the modified mesoporous carbon.

7. The method for producing spider protein fiber using spider protein according to claim 4, characterized in that: The raw material of the modified mesoporous carbon also includes isobutyramide; the weight ratio of the mesoporous carbon, the polyetherimide and the isobutyramide is 18:2:1-2.

8. The method for producing spider protein fiber using spider protein according to claim 1, characterized in that: The solvent is water and an organic solvent, and the organic solvent includes one of ethanol, acetone and isopropanol.

9. The method for producing spider protein fiber using spider protein according to claim 1, characterized in that: The preparation of the spinning solution comprises the following steps: S1, dispersing spider silk protein in a solvent and stirring to obtain a protein solution; S2. Add the remaining components to the protein solution, mix evenly, and stir to obtain a spinning solution.

10. The method for producing spider protein fiber using spider protein according to claim 9, characterized in that: In step S1, the stirring temperature is 50-60°C and the stirring time is 1-2h; in step S2, the stirring temperature is 80-90°C and the stirring time is 4-5h.

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