A collagen-natural polymer material composite fiber and preparation method thereof

Abstract

The present application relates to the field of new material technology, and specifically discloses a collagen-natural polymer material composite fiber and a preparation method thereof. A collagen-natural polymer material composite fiber comprises collagen aggregate solution and PVA polymer solution as raw materials, and the composite fiber is obtained after wet spinning; the preparation method is: preparing a collagen aggregate solution and mixing it with a PVA polymer material solution to obtain a spinning solution, and freeze-drying after wet spinning to obtain the composite fiber. The composition of the present application can be used for the preparation of clothing, and has the advantages of high protein content and good mechanical properties.

Description

Technical Field

[0001] The present application relates to the field of new material technology, and more specifically, to a collagen-natural polymer material composite fiber and a preparation method thereof. Background Art

[0002] Green and low-carbon development is the general trend of global sustainable development, and accelerating green transformation is even more urgent. Fashion is one of the industries with the greatest environmental damage at present, with environmental problems such as water pollution, carbon emissions, non-degradable chemicals, and excessive consumption and waste. Textile fibers are an indispensable part of the fashion industry, including natural fibers and synthetic fibers, among which the development of natural fibers is in line with the current new environmental protection concept. The manufacturing industry has environmental problems such as water pollution, carbon emissions, non-degradable chemicals, and excessive consumption and waste. Textile fibers are an indispensable part of the manufacturing industry, including natural fibers and synthetic fibers, among which the development of natural fibers is in line with the current new environmental protection concept.

[0003] With the gradual improvement of people's living standards, people's demand for textiles is no longer just the most basic requirements such as warmth and body covering. People's requirements for textiles in terms of beauty, comfort, antibacterial properties are also increasing day by day. Clothes made of natural fibers are becoming more and more popular. Natural fibers include animal fibers, plant fibers and artificial fibers. Among them, natural collagen fibers extracted from animal skins are a protein with a triple helix structure. Compared with plant proteins, collagen has better mechanical properties, moisturizing properties, antibacterial properties, etc., and can retain the properties of natural proteins to a certain extent. The prepared clothing has better skin affinity with the human body and can improve people's wearing comfort. However, pure collagen has strong water absorption and is easily degraded in solutions at higher temperatures, resulting in poor spinnability. In addition, due to the existing technology, the extraction rate of collagen is low, and its natural triple helix structure is easily dissolved into small molecule gelatin or even polypeptide chains and damaged, resulting in the prepared fibers being easy to break and having poor softness, which reduces the skin affinity and comfort of protein fibers. Summary of the invention

[0004] In order to increase the solid content of collagen in the fiber and obtain fibers with good breaking strength, the present application provides a collagen-natural polymer material composite fiber and a preparation method thereof.

[0005] In a first aspect, the present application provides a method for preparing collagen-natural polymer material composite fibers, using the following technical solution:

[0006] A method for preparing collagen-natural polymer material composite fibers, characterized in that it comprises the following steps:

[0007] (1) preparing a PVA solution: mixing it with water in a certain proportion and stirring to prepare a PVA polymer solution;

[0008] (2) preparing collagen-natural polymer composite fiber spinning solution: mixing the collagen aggregate solution and the prepared PVA polymer solution at a weight ratio of 1:(1-4), heating and stirring, adding a cross-linking agent, adjusting the solution pH, mixing and stirring, and defoaming to obtain the collagen-natural polymer composite fiber spinning solution;

[0009] (3) Wet spinning, forming, stretching and drying in a coagulation bath to obtain the collagen-natural polymer material composite fiber.

[0010] By adopting the above technical scheme, collagen has many advantages but its mechanical strength is poor and it is not easy to be spun. By combining it with PVA polymer which has good heat resistance, excellent mechanical properties and easy processing, the mechanical properties and spinnability of collagen fibers are improved to produce a skin-friendly composite fiber material with high breaking strength.

[0011] Optionally, the preparation method of the collagen aggregate is as follows:

[0012] (1) thoroughly cleaning the sheepskin scraps after meat removal, depilation and degreasing with distilled water, adding a strong acid solution for cleaning, and adjusting to a neutral state to obtain a raw leather;

[0013] (2) adding distilled water and an acidic solution to the processed raw leather in a weight ratio of 1:(50-60):(1-1.5), high-speed homogenization and crushing, centrifugation to collect the precipitate, and the mixed solution is used for later use;

[0014] (3) mixing the above mixed solution with a mixed solution of an acidic solution and its salt solution, wherein the ratio of the added amount of the mixed solution to the weight of the raw skin added is (20-30):1, mixing with the precipitate collected in step (2), dialyzing for 1-2 days, and freeze-drying to obtain a collagen aggregate sponge;

[0015] (4) After adding anionic ionic liquid and aggregate sponge in a weight ratio of (4.5-10):1, 100 ml of aqueous solution is added and heated to 50-80° C. for reaction. After the reaction is completed, the precipitate is collected by centrifugation and dialyzed for 1-2 days to obtain the collagen aggregate solution.

[0016] By adopting the above technical scheme, a strong acid solution is added to clean the sheepskin, the inorganic salt contained in the sheepskin is removed, the inorganic salt leaves the collagen and dissolves in the solution, and the raw sheepskin is swollen, which is beneficial to the subsequent operation steps, distilled water and the acidic solution are added to homogenize and break, the covalent bonds between collagen molecules or between other molecules are destroyed, and the salt bonds and Schiff bases between molecules are further destroyed, so that the collagen is fully dissolved in the acidic solution, and a mixed solution of the acidic solution and its salt solution is added. Under acidic conditions and the action of the salt solution, the dissolved collagen is gradually precipitated, and then small molecules are removed by dialysis operation to obtain a collagen aggregate sponge, anionic ionic liquid is added and mixed with the aggregate sponge to dissolve a part of the easily soluble collagen that cannot be used for textile processing, and the part of the protein and peptide chain dissolved into small molecules is further removed through dialysis to form a collagen aggregate solution, thereby retaining more collagen to the greatest extent.

[0017] Optionally, the strong acid solution in step (1) is any one of hydrochloric acid and sulfuric acid.

[0018] By adopting the above technical scheme, the positive ions of the inorganic salts in the sheepskin, such as sodium ions, potassium ions, etc., will be replaced by the hydrogen ions in the acid and become the corresponding acid salts, and the negative ions, such as chloride ions, sulfate ions, etc., will combine with the hydrogen ions to form water-soluble acids, so that the inorganic salts are dissolved in a strong acid solution for removal. Selecting strong acids with a higher degree of electrolysis, such as hydrochloric acid and sulfuric acid, is more conducive to reacting with the inorganic salts in the sheepskin for removal.

[0019] Optionally, the acidic solution in steps (2) and (3) is any one of oxalic acid and citric acid, and the acid salt solution in step (3) is any one of sodium chloride, sodium sulfate, sodium oxalate, sodium citrate, and sodium acetate.

[0020] By adopting the above technical scheme, the raw hide after preliminary treatment is immersed in a mixed solution of an acidic solution and its salt solution. On the one hand, the fat cell walls and ester glands in the raw hide are destroyed, impurities are further removed, and the fibers in the raw hide are stretched to enhance the flexibility of the fibers. On the other hand, under acidic conditions, the salt solution precipitates a part of the dissolved collagen, thereby increasing the collagen content in the finally obtained fibers.

[0021] Optionally, the mixing ratio of the acidic solution to its salt solution is 1:(1-2).

[0022] By adopting the above technical solution, as the amount of salt solution added increases, the precipitation of collagen increases, but excessive salt solution will cause excessive salt in the collagen precipitate, which will affect subsequent operations and result in low breaking strength of the prepared fiber.

[0023] Preferably, in step (2), the cross-linking agent is aluminum chloride, and the solution Ph is adjusted to between 3 and 5.

[0024] By adopting the above technical solution, when aluminum chloride is selected as the cross-linking agent and the Ph of the collagen-natural polymer composite fiber spinning solution is controlled between 3 and 5, the obtained fiber has good breaking strength and breaking elongation.

[0025] Preferably, in step (2), the cross-linking agent is glutaraldehyde, and the solution Ph is adjusted to between 8 and 10.

[0026] By adopting the above technical solution, when glutaraldehyde is selected as the cross-linking agent and the Ph of the collagen-natural polymer composite fiber spinning solution is controlled between 8 and 10, the obtained fiber has good breaking strength and breaking elongation.

[0027] Preferably, the preparation method further comprises step (4) as follows:

[0028] The dried fiber is immersed in a coagulation bath containing a titanium silicate microsphere solution and a sodium alginate solution, and then air-dried.

[0029] By adopting the above technical scheme, the prepared fiber is placed in a titanium silicate microsphere solution and a sodium alginate solution for modification so that the fiber has certain hydrophobicity and antibacterial ability, and can be used for the design of textile fabrics with special properties.

[0030] In a second aspect, the present application provides a collagen-natural polymer material composite fiber, which adopts the following technical solution:

[0031] A collagen-natural polymer material composite fiber, characterized in that it is prepared by the above-mentioned preparation method.

[0032] In summary, this application has the following beneficial effects:

[0033] 1. Since the collagen extraction method adopted in this application is different from the traditional extraction method with low collagen extraction rate and serious collagen denaturation, the impurity components in the sheepskin that cause poor fiber performance are gradually removed by processing the raw materials, thereby greatly improving the extraction efficiency of collagen in the raw sheepskin. The collagen obtained retains its excellent properties, is stable and has a natural structure. The final fiber protein content is high and the breaking strength is high.

[0034] 2. In this application, non-toxic, harmless, biodegradable natural polymer PVA material is preferably used to blend with the prepared collagen aggregate solution, which improves the spinnability of collagen. By selecting a suitable cross-linking agent to control the Ph of the solution, a composite fiber with high collagen content, good spinnability and good mechanical properties is finally obtained.

[0035] 3. The collagen composite fiber prepared in this application is skin-friendly and biodegradable, and can be used as a substitute for chemical fibers based on graphite as raw materials. It is a green and sustainable process.

[0036] 4. The present application further performs functional modification on the fiber during the coagulation bath process, giving the fiber better antibacterial and hydrophobic properties, so that it has a wider application scenario. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 It is a flow chart of the method provided by this application. DETAILED DESCRIPTION

[0038] The present application is further described in detail below with reference to the embodiments.

[0039] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. If the manufacturers of the reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0040] 1-Butyl-3-methylimidazolium chloride was purchased from Jinan Henghan Chemical Co., Ltd., CAS: 79917-90-1; PVA material was purchased from Jiangsu Anchuang New Materials Co., Ltd., brand: 32-80.

[0041] Preparation examples of raw materials and / or intermediates

[0042] Preparation Example 1

[0043] A collagen aggregate, the preparation method is as follows:

[0044] (1) 200 g of sheepskin scraps that have been subjected to fleshing, depilation and degreasing treatments are thoroughly cleaned with distilled water, added to a 3% by mass hydrochloric acid solution for treatment and cleaning, and then washed with distilled water until neutral to obtain a raw leather;

[0045] (2) adding 10 kg of distilled water and 200 g of 2% oxalic acid solution to the processed raw leather in a weight ratio of 1:50:1, high-speed homogenization and crushing, collecting the precipitate after centrifugation, and separating the mixed solution for use;

[0046] (3) the mixed solution was mixed with 4 kg of a 2% mixed solution of oxalic acid solution and sodium oxalate prepared by mixing in a ratio of 1:1, stirred for reaction for 12 h, mixed with the precipitate collected in step (2), dialyzed for 1 day, and freeze-dried to obtain a collagen aggregate sponge;

[0047] (4) After adding 900 g of 1-butyl-3-methylimidazolium chloride and mixing with the aggregate sponge, 100 ml of an aqueous solution was added and heated to 50° C. for reaction. After the reaction was completed, the precipitate was collected by centrifugation and dialyzed for 2 days to obtain the collagen aggregate solution.

[0048] Preparation Example 2

[0049] A collagen aggregate, the preparation method is as follows:

[0050] (1) 200 g of sheepskin scraps that have been subjected to fleshing, depilation and degreasing treatments are thoroughly cleaned with distilled water, added to a 3% by mass sulfuric acid solution for treatment and cleaning, and then washed with distilled water until neutral to obtain a raw leather;

[0051] (2) adding 12 kg of distilled water and 300 g of 2% oxalic acid solution in a weight ratio of 1:60:1.5 to the processed raw leather, high-speed homogenization and crushing, collecting the precipitate after centrifugation, and separating the mixed solution for use;

[0052] (3) the mixed solution was mixed with 4 kg of a 2% mixed solution of oxalic acid solution and sodium oxalate prepared by mixing in a ratio of 1:2, stirred for reaction for 12 h, mixed with the precipitate collected in step (2), dialyzed for 2 days, and freeze-dried to obtain a collagen aggregate sponge;

[0053] (4) After adding 2 kg of 1-butyl-3-methylimidazolium chloride and mixing with the aggregate sponge, 100 ml of an aqueous solution was added and heated to 50° C. for reaction. After the reaction was completed, the precipitate was collected by centrifugation and dialyzed for 2 days to obtain the collagen aggregate solution.

[0054] Preparation Example 3

[0055] A collagen aggregate, the preparation method is as follows:

[0056] (1) 200 g of sheepskin scraps that have been subjected to fleshing, depilation and degreasing treatments are thoroughly cleaned with distilled water, added to a 3% by mass sulfuric acid solution for treatment and cleaning, and then washed with distilled water until neutral to obtain a raw leather;

[0057] (2) adding 11 kg of distilled water and 240 g of a 2% sodium oxalate solution to the processed raw leather in a weight ratio of 1:55:1.2, high-speed homogenization and crushing, collecting the precipitate after centrifugation, and separating the mixed solution for use;

[0058] (3) The mixed solution was mixed with 6 kg of a 2% mixed solution of oxalic acid solution and sodium chloride prepared by mixing in a ratio of 1:1.5, stirred for reaction for 12 h, mixed with the precipitate collected in step (2), dialyzed for 2 days, and freeze-dried to obtain a collagen aggregate sponge; (4) 1.5 kg of 1-ethyl-3-methylimidazolium bromide was added to the aggregate sponge, and then 100 ml of an aqueous solution was added and heated to 60° C. for reaction. After the reaction was completed, the precipitate was collected by centrifugation and dialyzed for 2 days to obtain the collagen aggregate solution.

[0059] Preparation Example 4

[0060] A collagen aggregate, the preparation method is as follows:

[0061] (1) 200 g of sheepskin scraps that have been subjected to fleshing, depilation and degreasing treatments are thoroughly cleaned with distilled water, added to a 3% by mass hydrochloric acid solution for treatment and cleaning, and then washed with distilled water until neutral to obtain a raw leather;

[0062] (2) adding 10 kg of distilled water and 240 g of 2% acetic acid solution in a weight ratio of 1:50:1.2 to the processed raw leather, high-speed homogenization and crushing, collecting the precipitate after centrifugation, and separating the mixed solution for use;

[0063] (3) The above mixed solution was mixed with 4 kg of a 2% mixed solution of oxalic acid solution and sodium oxalate prepared by mixing in a ratio of 1:1.5, stirred for reaction for 12 h, mixed with the precipitate collected in step (2), dialyzed for 1 day, and freeze-dried to obtain a collagen aggregate sponge; (4) 1.06 kg of 1-ethyl-3-methylimidazolium bromide was added to the aggregate sponge, and then 100 ml of an aqueous solution was added and heated to 50° C. for reaction. After the reaction was completed, the precipitate was collected by centrifugation and dialyzed for 2 days to obtain the collagen aggregate solution.

[0064] Comparative Preparation Example 1

[0065] A collagen aggregate, which is different from Preparation Example 1 in that the ratio of oxalic acid to sodium oxalate added in this Preparation Example is 1:3.

[0066] Example

[0067] Example 1

[0068] A collagen-natural polymer material composite fiber is prepared by the following steps:

[0069] (1) Preparing a PVA solution: 150 g of high molecular weight PVA and 850 g of water were mixed and stirred to dissolve to prepare a PVA high molecular weight solution with a concentration of 15%;

[0070] (2) Preparing collagen-natural polymer composite fiber spinning solution: 0.25 kg of the collagen aggregate solution prepared in Preparation Example 1 was mixed with 1 kg of the PVA polymer solution, stirred at 55° C. for 5 h, a 5% boric acid solution cross-linking agent was added, the solution pH was adjusted to 3, the mixture was stirred for 20 min, and the spinning solution of collagen-natural polymer composite fibers was obtained by defoaming;

[0071] (3) Wet spinning, the spinning solution is extruded at a certain speed through a micro-injection pump, and the spinning solution is formed, stretched and dried at 45° C. in a coagulation bath filled with saturated sodium sulfate to obtain the collagen-natural polymer material composite fiber.

[0072] Example 2

[0073] A collagen-natural polymer material composite fiber, which is different from Example 1 in that 250g of collagen aggregate solution and 250g of PVA polymer solution are added in this example, and the addition ratio is 1:1.

[0074] Example 3

[0075] A collagen-natural polymer material composite fiber, which is different from Example 1 in that 250g of collagen aggregate solution and 750g of PVA polymer solution are added in this example, and the addition ratio is 1:3.

[0076] Example 4

[0077] A collagen-natural polymer material composite fiber, which is different from Example 1 in that the collagen aggregate solution prepared in Preparation Example 2 is added in this example.

[0078] Example 5

[0079] A collagen-natural polymer material composite fiber, which is different from Example 1 in that the collagen aggregate solution prepared in Preparation Example 3 is added in this example.

[0080] Example 6

[0081] A collagen-natural polymer material composite fiber, which is different from Example 1 in that the collagen aggregate solution prepared in Preparation Example 4 is added in this example.

[0082] Example 7

[0083] A collagen-natural polymer material composite fiber, which is different from Example 6 in that the cross-linking agent added in this example is 5% aluminum chloride solution.

[0084] Example 8

[0085] A collagen-natural polymer material composite fiber, which is different from Example 7 in that the Ph of the solution in this embodiment is adjusted to 5.

[0086] Example 9

[0087] A collagen-natural polymer material composite fiber, which is different from Example 8 in that the cross-linking agent added in this example is a 5% glutaraldehyde solution.

[0088] Example 10

[0089] A collagen-natural polymer material composite fiber, which is different from Example 9 in that the Ph of the solution in this example is adjusted to 8.

[0090] Embodiment 11

[0091] A collagen-natural polymer material composite fiber, which is different from Example 9 in that the Ph of the solution in this embodiment is adjusted to 10.

[0092] Example 12

[0093] A collagen-natural polymer composite fiber, which is different from Example 8 in that this embodiment also includes a step of modifying the fiber, as follows:

[0094] Weigh 2.39 g of titanium sulfate and 17.30 g of hexadecyltrimethylsilane, add 30 mL of ethanol and 30 mL of aqueous solution, mix, and mechanically stir for 1 hour to obtain a titanium silicate microsphere solution; the dried fiber is placed in a coagulation bath containing titanium silicate microspheres and a 3% sodium alginate solution and immersed for 40 minutes for modification. After the modification is completed, the fiber is wound, collected, and dried.

[0095] Comparative Example

[0096] Comparative Example 1

[0097] A collagen-natural polymer composite fiber, which is different from Example 1 in that the specific preparation steps are as follows: (1) 200 g of sheepskin scraps that have been subjected to flesh removal, depilation, and degreasing treatments are thoroughly cleaned with distilled water to obtain a raw leather;

[0098] (2) mixing the raw leather with 900 g of anionic ionic liquid 1-butyl-3-methylimidazolium chloride, heating to 140° C. under magnetic stirring for a certain period of time, and centrifuging at high speed while hot to obtain a transparent collagen / ionic liquid solution and undissolved collagen;

[0099] (3) collecting the obtained collagen / ion solution, adding an appropriate amount of ethanol to soak for 2 h, centrifuging the generated white flocculent precipitate, washing and drying to obtain the extracted collagen powder;

[0100] (4) taking 250 g of the prepared collagen powder and mixing it with 1 kg of the prepared PVA polymer solution to obtain a spinning solution;

[0101] (5) Wet spinning, the spinning solution is extruded at a certain speed through a micro-injection pump, and the spinning solution is formed, stretched and dried at 45° C. in a coagulation bath filled with saturated sodium sulfate to obtain the collagen-natural polymer material composite fiber.

[0102] Comparative Example 2

[0103] A collagen-natural polymer material composite fiber, which is different from Example 1 in that the collagen aggregate solution prepared in Comparative Preparation Example 1 is added to this comparative example.

[0104] Comparative Example 3

[0105] A collagen-natural polymer material composite fiber, which is different from Example 12 in that the fiber prepared in Comparative Example 1 is used for modification in this comparative example.

[0106] Comparative Example 4

[0107] A collagen-natural polymer material composite fiber, which is different from Example 7 in that the Ph of the adjusted solution in this comparative example is 8.

[0108] Performance testing

[0109] Detection method / test method

[0110] Detection of protein content in composite fibers: Examples 1-12 and Comparative Examples 1-4 were tested. 20 ml of spinning solution prepared by the preparation methods described in Examples 1-12 and Comparative Examples 1-4 were taken, and the sample obtained after spinning and drying was weighed, and its weight was recorded as b. 20 ml of the prepared PVA polymer solution was selected, and weighed after spinning and drying, and its weight was recorded as a. The formula for calculating the collagen content is as follows:

[0111]

[0112] Breaking strength and elongation test: Model YG061 electronic single yarn strength tester is used to test the breaking strength of the fiber. A single sample fiber is clamped on the single fiber electronic strength tester with a clamping length of 250mm. The sample is stretched at a stretching speed of 500mm / min until the fiber breaks. The data is recorded. Each sample is tested for 20 strands, and the average value is taken to calculate the breaking strength and breaking elongation.

[0113] Table 1

[0114]

[0115]

[0116] It can be seen from Examples 1-3 and Comparative Example 1 and Table 1 that the experimental data of Examples 1-3 are better than those of Comparative Example 1, indicating that the collagen extracted using the existing extraction method will be partially dissolved into small molecules and peptide chains during the textile process, so that the final fiber has low breaking strength and low collagen content. Compared with the prior art, the fibers prepared in this application have a higher collagen content, which improves comfort and skin-friendliness while having better stability, is not easy to break, and has high breaking strength.

[0117] Combining Examples 1-3 with Comparative Example 2 and Table 1, it can be seen that the test data of Examples 1-3 are all better than those of Comparative Example 2, indicating that adding too much salt solution in the process of preparing the collagen aggregate solution will cause the retention of impurity ions in the fibers, resulting in a decrease in the mechanical properties of the obtained fibers and affecting the protein content in the fibers.

[0118] Combining Examples 7-8 with Comparative Example 4 and Table 1, it can be seen that the test data of Examples 7-8 are better than those of Comparative Example 3, indicating that when aluminum chloride solution is used as a cross-linking agent and the solution Ph is set at 3-5, the collagen aggregate solution and the PVA polymer solution have better cross-linking properties, and the obtained fibers have better mechanical properties and a higher protein content.

[0119] It can be seen from Examples 1-6 and Table 1 that Examples 1-6 all have good performance, indicating that the present application can be used in combination with Examples 6-11 and Table 1. When aluminum chloride and glutaraldehyde are used as cross-linking agents in the process of preparing the fiber, the fiber has better performance. It can be seen from Examples 7-8 that when aluminum chloride is used as a cross-linking agent, the Ph of the solution is regulated between 3-5, and the obtained fiber has the best performance; and from Examples 9-11 and Table 1, it can be seen that when glutaraldehyde is used as a cross-linking agent, the Ph of the solution needs to be regulated between 8-10, and the obtained fiber has better mechanical properties.

[0120] Combining Example 8 with Example 12 and Table 1, it can be seen that the various test data of Example 12 are better than those of Example 8, indicating that the modified fiber has better mechanical properties.

[0121] Antibacterial property: Examples 10 and 12 and Comparative Example 3 were tested for antibacterial property. The antibacterial property of the fiber was tested using Staphylococcus aureus according to the test method in GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method";

[0122] Hydrophobicity test: Add distilled water drops on the fiber surface and let it stand to observe the hydrophobicity, and use a contact angle meter to test the contact angle of the sample.

[0123] Table 2

[0124] Example 10 Example 12 Comparative Example 3 Antibacterial rate / % 85.76 92.18 77.37 Water contact angle° 100.64 120.15 85.46

[0125] Combining Example 12 with Comparative Example 3 and Table 1-2, it can be seen that the various properties of Example 12 are better than those of Comparative Example 3, indicating that the fiber prepared by the method of the present application has better modification performance, and its antibacterial property and hydrophobicity are better than those of Comparative Example 3. Combining Example 10 with Example 12 and Table 1-2, it can be shown that natural protein fiber has good antibacterial properties, and after modification, its antibacterial properties are improved while giving the fiber hydrophobic properties, further expanding the application scenarios of the fiber.

[0126] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A method for preparing collagen-natural polymer material composite fibers, characterized in that: The steps include: a. Preparation of PVA solution: mixing it with water in a certain proportion and stirring to prepare a PVA polymer solution; b. Preparing collagen-natural polymer composite fiber spinning solution: mixing the collagen aggregate solution with the prepared PVA polymer solution at a weight ratio of 1: (1-4), heating and stirring, adding a crosslinking agent, adjusting the solution Ph, mixing and stirring, and defoaming to obtain a collagen-natural polymer composite fiber spinning solution; c. Wet spinning, forming, stretching and drying in a coagulation bath to obtain the collagen-natural polymer composite fiber; In step b, the cross-linking agent is aluminum chloride, and the solution Ph is adjusted to between 3 and 5; The preparation method further comprises step d as follows: The dried fiber is immersed in a coagulation bath containing a titanium silicate microsphere solution and a sodium alginate solution, and then air-dried; The preparation method of the collagen aggregate is as follows: (1) The sheepskin scraps that have been fleshed, dehaired and defatted are thoroughly cleaned with distilled water, treated with a strong acid solution, and then washed with distilled water until they are neutral to obtain raw leather; (2) Add distilled water and acid solution to the processed raw leather in a weight ratio of 1: (50-60): (1-1.5), homogenize at high speed, collect the precipitate by centrifugation, and keep the mixed solution for later use; (3) The mixed solution is mixed with a mixed solution of an acidic solution and a salt solution, the ratio of the amount of the mixed solution added to the weight of the raw skin added is (20-30):1, the collagen dissolved in the mixed solution is gradually precipitated, mixed with the precipitate collected in step (2) and dialyzed for 1-2 days, and freeze-dried to obtain a collagen aggregate sponge; (4) After adding anionic ionic liquid and aggregate sponge in a weight ratio of (4.5-10):1, 100 ml of aqueous solution is added and heated to 50-80° C. for reaction. After the reaction is completed, the precipitate is collected by centrifugation and dialyzed for 1-2 days to obtain the collagen aggregate solution.

2. The method for preparing a collagen-natural polymer material composite fiber according to claim 1, characterized in that: The strong acid solution in step (1) is any one of hydrochloric acid and sulfuric acid.

3. The method for preparing a collagen-natural polymer material composite fiber according to claim 1, characterized in that: The acidic solution in steps (2) and (3) is any one of oxalic acid and citric acid, and the acid salt solution in step (3) is any one of sodium chloride, sodium sulfate, sodium oxalate, sodium citrate, and sodium acetate.

4. The method for preparing a collagen-natural polymer material composite fiber according to claim 1, characterized in that: The mixing ratio of the acid solution to its salt solution is 1:(1-2).

5. The method for preparing a collagen-natural polymer material composite fiber according to claim 1, characterized in that: In step b, the cross-linking agent is glutaraldehyde, and the solution pH is adjusted to between 8 and 10.

6. A collagen-natural polymer material composite fiber, characterized in that: The method is prepared according to any one of claims 1 to 4.

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