High-strength bio-based protein silk and preparation method thereof

Abstract

The invention relates to the technical field of protein fibers, and provides high-strength bio-based protein silk and a preparation method thereof, and the high-strength bio-based protein silk is prepared by weaving imitated silk; the bio-based protein silk is prepared by weaving imitated silk; the imitated silk is prepared from the following components in parts by weight: 60-80 parts of polyvinyl alcohol, 45-60 parts of collagen, 1-3 parts of a cross-linking agent, 1-3 parts of a defoaming agent and 8-16 parts of an auxiliary A, the auxiliary agent A comprises the following components in parts by weight: 4-8 parts of titanium dioxide, 4-8 parts of mica and 1-2 parts of nicotinic acid compounds. According to the technical scheme, the problem that the bio-based protein silk in the prior art is low in strength is solved.

Description

Technical Field

[0001] The present invention relates to the technical field of protein fibers, and in particular to high-strength bio-based protein silk and a preparation method thereof. Background Art

[0002] Bio-based protein silk, a green alternative to traditional silk, has shown broad application prospects in textiles, bioengineering, and other fields. It is typically produced using plant or microbial proteins as raw materials, using a spinning process that mimics the fiber structure and properties of natural silk.

[0003] However, current imitation silk products generally have the problem of insufficient strength, which seriously restricts their industrial application. The high strength of natural silk comes from the orderly arrangement of silk fibroin molecules and the stable construction of β-folded structure. However, during the spinning process, bio-based proteins are difficult to form a similar dense structure due to the low molecular weight of the raw materials and weak intermolecular forces. In the existing technology, although the fiber strength is improved by chemical cross-linking, physical stretching and other methods, it is often accompanied by disadvantages such as reduced protein activity and complex processes, which cannot meet the use requirements of high-end textile fabrics, load-bearing biological scaffolds and other scenarios. Therefore, it is necessary to develop a technical solution that can effectively improve the strength of bio-based protein silk imitation silk. Summary of the Invention

[0004] The present invention provides high-strength bio-based protein silk and a preparation method thereof, which solves the problem of poor strength of imitation silk in bio-based protein silk in the related art.

[0005] The technical solutions of the present invention are as follows: The present invention provides high-strength bio-based protein silk, which is made by imitating silk weaving; The raw materials of the silk include the following components in parts by weight: 60-80 parts of polyvinyl alcohol, 45-60 parts of collagen, 1-3 parts of a cross-linking agent, 1-3 parts of a defoaming agent, and 8-16 parts of an auxiliary agent A; The auxiliary agent A comprises the following components in parts by weight: 4-8 parts of titanium dioxide, 4-8 parts of mica, and 1-2 parts of nicotinic acid compounds.

[0006] As a further technical solution, the preparation method of the auxiliary agent A includes the following steps: mixing the components of the auxiliary agent A to obtain the auxiliary agent A.

[0007] As a further technical solution, the preparation method of the auxiliary agent A comprises the following steps: A1. dissolving a nicotinic acid compound to obtain a solution; A2. Mix titanium dioxide, mica and the dissolving solution, and dry to obtain auxiliary agent A.

[0008] As a further technical solution, the stirring speed during the mixing is 500-700 rpm, and the time is 25-35 min.

[0009] As a further technical solution, the solvent during the dissolving includes an alcohol solvent. The mass ratio of the nicotinic acid compound and the alcohol solvent is 1:20-35.

[0010] As a further technical solution, the nicotinic acid compound includes 6-sulfonic acid nicotinic acid and / or 2-phenyl isonicotinic acid.

[0011] As a further technical solution, when the nicotinic acid compound is 6-sulfonic acid nicotinic acid and 2-phenyl isonicotinic acid, the mass ratio of the 6-sulfonic acid nicotinic acid and the 2-phenyl isonicotinic acid is 5:5-8:2.

[0012] As a further technical solution, the preparation method of the silk-like silk includes the following steps: S1, dissolving collagen to obtain a collagen solution; S2, mixing the collagen solution and a defoaming agent, adding a polyvinyl alcohol solution for continuous mixing, and then adding the remaining components for mixing to obtain a spinning solution, spinning, and obtaining silk-like silk.

[0013] As a further technical solution, the crosslinking agent includes one or more of formaldehyde, glutaraldehyde, and dibenzoyl peroxide. The components of the defoaming agent include sodium phosphate, sodium hydroxide, and acetamide at a mass ratio of 1:0.1:1-3.

[0014] As a further technical solution, the post-processing includes, in sequence, heat treatment, finishing, drying, curling, heat setting, and cutting treatment.

[0015] The application also provides a preparation method of high-strength bio-based protein silk, which is used for preparing the high-strength bio-based protein silk and includes the following steps: weaving the silk-like silk to obtain the bio-based protein silk.

[0016] The working principle and beneficial effects of the application are as follows: In the present invention, nicotinic acid compounds are added to the imitation silk raw materials. During the preparation process of the imitation silk, the nicotinic acid compounds connect titanium dioxide, mica, and polyvinyl alcohol, improving the compatibility between the components. This allows the titanium dioxide and mica to be evenly dispersed in the polyvinyl alcohol matrix, avoiding agglomeration. The evenly dispersed titanium dioxide, thanks to its high hardness, and the mica, thanks to its interlayer slip and crack-blocking capabilities of its flaky structure, work closely with the polyvinyl alcohol matrix. This makes the prepared imitation silk less prone to breakage during the weaving process, and the resulting fabric has higher strength. Compared to traditional imitation silk, the imitation silk of the present invention can more effectively resist deformation and damage when subjected to external forces such as tension and friction. DETAILED DESCRIPTION

[0017] 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 embodiments described 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 making any creative efforts are within the scope of protection of the present invention.

[0018] In the following examples and comparative examples, the weight average molecular weight of polyvinyl alcohol is 60,000, the particle size of titanium dioxide is 50 nm, the particle size of mica is 5 μm, and the defoaming agent is sodium phosphate, sodium hydroxide, and acetamide in a mass ratio of 1:0.1:3.

[0019] Example 1 High-strength bio-based protein silk, bio-based protein silk is made by imitating silk weaving; The raw materials of silk include the following components in parts by weight: 60 parts of polyvinyl alcohol, 45 parts of collagen, 1 part of glutaraldehyde, 1 part of degassing agent, and 8 parts of auxiliary agent A; The auxiliary agent A comprises the following components in parts by weight: 4 parts of titanium dioxide, 4 parts of mica, and 1 part of 6-sulfonic acid nicotinic acid; The preparation method of the auxiliary agent A comprises the following steps: mixing the components of the auxiliary agent A (stirring speed during mixing is 500 rpm and time is 35 minutes) to obtain the auxiliary agent A; The preparation method of imitation silk comprises the following steps: S1, dissolving collagen to obtain a collagen solution; S2, mixing the collagen solution and the defoaming agent, adding the polyvinyl alcohol solution and continuing to mix, then adding the remaining components and mixing to obtain a spinning solution, spinning (spinning viscosity 550 centipoise), heat treating, finishing, drying, curling, heat setting, and cutting to obtain imitation silk; The high-strength bio-based protein silk comprises the following steps: weaving imitation silk to obtain the bio-based protein silk.

[0020] Example 2 High-strength bio-based protein silk, bio-based protein silk is made by imitating silk weaving; The raw materials of silk include the following components in parts by weight: 80 parts of polyvinyl alcohol, 60 parts of collagen, 3 parts of glutaraldehyde, 3 parts of degassing agent, and 16 parts of auxiliary agent A; The auxiliary agent A comprises the following components in parts by weight: 8 parts of titanium dioxide, 8 parts of mica, and 2 parts of 6-sulfonic acid nicotinic acid; The preparation method of the auxiliary agent A comprises the following steps: mixing the components of the auxiliary agent A (stirring speed during mixing is 700 rpm and time is 25 min) to obtain the auxiliary agent A; The preparation method of imitation silk comprises the following steps: S1, dissolving collagen to obtain a collagen solution; S2, mixing the collagen solution and the defoaming agent, adding the polyvinyl alcohol solution and continuing to mix, then adding the remaining components and mixing to obtain a spinning solution, spinning (spinning viscosity 550 centipoise), heat treating, finishing, drying, curling, heat setting, and cutting to obtain imitation silk; The high-strength bio-based protein silk comprises the following steps: weaving imitation silk to obtain the bio-based protein silk.

[0021] Example 3 High-strength bio-based protein silk, bio-based protein silk is made by imitating silk weaving; The raw materials of silk include the following components in parts by weight: 70 parts of polyvinyl alcohol, 50 parts of collagen, 2 parts of glutaraldehyde, 2 parts of defoaming agent, and 10 parts of auxiliary agent A; The additive A comprises the following components in parts by weight: 5 parts of titanium dioxide, 5 parts of mica, and 1.5 parts of 6-sulfonic acid nicotinic acid; The preparation method of the auxiliary agent A comprises the following steps: mixing the components of the auxiliary agent A (stirring speed during mixing is 600 rpm and time is 30 minutes) to obtain the auxiliary agent A; The preparation method of imitation silk comprises the following steps: S1, dissolving collagen to obtain a collagen solution; S2, mixing the collagen solution and the defoaming agent, adding the polyvinyl alcohol solution and continuing to mix, then adding the remaining components and mixing to obtain a spinning solution, spinning (spinning viscosity 550 centipoise), heat treating, finishing, drying, curling, heat setting, and cutting to obtain imitation silk; The high-strength bio-based protein silk comprises the following steps: weaving imitation silk to obtain the bio-based protein silk.

[0022] Example 4 The only difference between this embodiment and embodiment 3 is that the preparation method of auxiliary agent A comprises the following steps: A1. Dissolving 6-sulfonicotinic acid in ethanol (6-sulfonicotinic acid:ethanol mass ratio is 1:30) to obtain a solution; A2. Titanium dioxide, mica, and the dissolving solution were mixed (stirring speed during mixing was 600 rpm for 30 min), and dried to obtain additive A.

[0023] Example 5 The only difference between this example and Example 4 is that 6-sulfonic acid nicotinic acid is replaced by 2-phenylisonicotinic acid.

[0024] Example 6 The only difference between this example and Example 4 is that 6-sulfonicotinic acid is replaced by a composite modifier; the composite modifier comprises 6-sulfonicotinic acid and 2-phenylisonicotinic acid in a mass ratio of 5:5.

[0025] Example 7 The only difference between this example and Example 4 is that 6-sulfonicotinic acid is replaced by a composite modifier; the composite modifier comprises 6-sulfonicotinic acid and 2-phenylisonicotinic acid in a mass ratio of 8:2.

[0026] Comparative Example 1 The only difference between this comparative example and Example 3 is that the auxiliary agent A comprises the following components in parts by weight: 5 parts of titanium dioxide and 5 parts of mica.

[0027] The imitation silk obtained in Examples 1 to 7 and Comparative Example 1 was tested for performance: Strength: The breaking strength test was conducted in accordance with the standard GB / T 14337-2022 "Test method for tensile properties of chemical staple fibers"; the results are shown in Table 1 below.

[0028] Table 1 Test results

[0029] Compared with Comparative Example 1, the wet breaking strength of the imitation silk prepared in Examples 1 to 7 is higher, indicating that the addition of nicotinic acid compounds to the imitation silk significantly improves the breaking strength of the imitation silk, thereby improving the strength of the bio-based protein silk.

[0030] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. High-strength bio-based protein silk, characterized by: The bio-based protein silk is made by imitating silk weaving; The silk-like raw materials include the following components in parts by weight: 60-80 parts of polyvinyl alcohol, 45-60 parts of collagen, 1-3 parts of a cross-linking agent, 1-3 parts of a defoaming agent, and 8-16 parts of an auxiliary agent A; The auxiliary agent A comprises the following components in parts by weight: 4-8 parts of titanium dioxide, 4-8 parts of mica, and 1-2 parts of nicotinic acid compounds.

2. The high-strength bio-based protein silk according to claim 1, characterized in that The preparation method of the auxiliary agent A comprises the following steps: mixing the components of the auxiliary agent A to obtain the auxiliary agent A.

3. The high-strength bio-based protein silk according to claim 1, characterized in that: The preparation method of the auxiliary agent A comprises the following steps: A1. dissolving a nicotinic acid compound to obtain a solution; A2. Mix titanium dioxide, mica and the dissolving solution, and dry to obtain auxiliary agent A.

4. The high-strength bio-based protein silk according to claim 2 or 3, characterized in that: The stirring speed during the mixing is 500-700 rpm, and the time is 25-35 min.

5. The high-strength bio-based protein silk according to claim 3, characterized in that: The solvent used in the dissolution includes an alcohol solvent; The mass ratio of the nicotinic acid compound to the alcohol solvent is 1:20-35.

6. The high-strength bio-based protein silk according to claim 1, characterized in that The nicotinic acid compounds include 6-sulfonic acid nicotinic acid and / or 2-phenylisonicotinic acid.

7. The high-strength bio-based protein silk according to claim 1, characterized in that: When the nicotinic acid compounds are 6-sulfonic acid nicotinic acid and 2-phenylisonicotinic acid, the mass ratio of 6-sulfonic acid nicotinic acid to 2-phenylisonicotinic acid is 5:5 to 8:

2.

8. The high-strength bio-based protein silk according to claim 1, characterized in that: The method for preparing the imitation silk comprises the following steps: S1, dissolving collagen to obtain a collagen solution; S2. Mixing the collagen solution and the defoaming agent, adding the polyvinyl alcohol solution and continuing to mix, then adding the remaining components and mixing to obtain a spinning solution, spinning, and post-processing to obtain imitation silk.

9. The high-strength bio-based protein silk according to claim 8, characterized in that: The cross-linking agent includes one or more of formaldehyde, glutaraldehyde, and dibenzoyl peroxide; The defoaming agent comprises sodium phosphate, sodium hydroxide and acetamide in a mass ratio of 1:0.1:1-3; The post-processing includes heat treatment, finishing, drying, curling, heat setting and cutting in sequence.

10. A method for preparing high-strength bio-based protein silk, for preparing the high-strength bio-based protein silk according to any one of claims 1 to 9, characterized in that: The following steps are involved: The imitation silk is woven to obtain the bio-based protein silk.

Images