High-strength bio-based milk protein fiber and preparation method thereof
By adding modified cellulose nanofibers and flame retardants, the problem of insufficient strength of milk protein fibers was solved, and high-strength bio-based milk protein fibers were prepared, which are suitable for outdoor clothing and other scenarios.
Patent Information
- Application Number
- CN202510989324.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-17
- Publication Date
- 2025-09-12
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
Existing milk protein fibers lack strength, which limits their application in scenarios requiring endurance, such as outdoor clothing.
By adding modified cellulose nanofibers and flame retardants, the dispersibility and bonding strength of cellulose nanofibers are improved to prepare high-strength bio-based milk protein fibers.
The mechanical strength and flame retardant properties of bio-based milk protein fibers are significantly improved, making them suitable for scenarios requiring endurance, such as outdoor clothing.
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Abstract
Description
Technical Field
[0001] The present invention relates to the field of fiber technology, and in particular to high-strength bio-based milk protein fiber and a preparation method thereof. Background Art
[0002] In the textile fiber family, natural fibers and regenerated fibers have long occupied an important position. With the increasing demand of consumers for skin-friendliness and functionality, regenerated fibers made from natural proteins have gradually become a research hotspot, and milk protein fiber is a very representative one. It uses high-quality proteins such as casein in milk as raw materials. After dissolution and spinning, it is compounded with polymer materials such as cellulose or polyvinyl alcohol. It not only retains the biocompatibility of natural proteins, but also gives the fiber spinnability and practicality. However, due to the weak interaction between protein molecular chains and the fact that excessive cross-linking is often avoided during the spinning process to retain biological activity, the tensile strength of milk protein fibers is low, and they are prone to problems such as snagging and wear. Their application is limited in scenarios where tolerance is required, such as outdoor clothing. Therefore, it is necessary to propose a high-strength bio-based milk protein fiber. Summary of the Invention
[0003] The present invention provides high-strength bio-based milk protein fiber and a preparation method thereof, which solves the problem of insufficient strength of milk protein fiber in the prior art.
[0004] The technical solutions of the present invention are as follows: The present invention proposes a high-strength bio-based milk protein fiber, comprising the following raw materials in parts by weight: 70-80 parts of milk casein, 6-10 parts of bovine collagen, 1-5 parts of polyvinyl alcohol, 2-5 parts of modified cellulose nanofibers, 1-2.5 parts of a cross-linking agent, 1.5-3 parts of a defoaming agent, and 210-250 parts of water; the modified cellulose nanofibers are obtained by modifying cellulose nanofibers with an aromatic-substituted oxygen-containing compound.
[0005] As a further technical solution, the mass ratio of the aromatic substituted oxygen-containing compound to the cellulose nanofibers in the raw material of the modified cellulose nanofibers is 7-9:100.
[0006] In the high-strength bio-based milk protein fiber of the present invention, when the mass ratio of the aromatic substituted oxygen-containing compound to the cellulose nanofiber is lower than 7:100, the dispersibility of the cellulose nanofiber will be limited due to insufficient modification; when it is higher than 9:100, the dispersibility will also decrease; and when the mass ratio of the aromatic substituted oxygen-containing compound to the cellulose nanofiber is in the range of 7~9:100, the modification can be fully and uniformly achieved, while retaining the original structure and performance advantages of the cellulose nanofiber, its dispersibility is effectively improved.
[0007] As a further technical solution, the aromatic substituted oxygen-containing compound includes one or more of 2-benzylpropionic acid, 2-benzylpropane-1,3-diol, and 2-(hydroxymethyl)-2-phenylpropane-1,3-diol.
[0008] As a further technical solution, the cellulose nanofibers have a width of 10-50 nm and a length of 0.5-3 μm.
[0009] In the high-strength bio-based milk protein fiber of the present invention, if the cellulose nanofiber width is less than 10nm and the length is less than 0.5μm, the overlapping ability between fibers will be weakened due to excessive fragmentation, making it difficult to form a stable network structure, affecting the bonding strength with the milk protein fiber; if the cellulose nanofiber width is greater than 50nm and the length is greater than 3μm, it is more likely to have problems such as uneven fiber dispersion and serious agglomeration; the cellulose nanofiber width is 10~50nm and the length is 0.5~3μm, which enables the cellulose nanofiber to construct a three-dimensional network with both strength and toughness through a moderate aspect ratio, thereby further improving the mechanical strength of the high-strength bio-based milk protein fiber.
[0010] As a further technical solution, a method for preparing modified cellulose nanofibers includes the following steps: dissolving an aromatic substituted oxygen-containing compound in anhydrous ethanol, adding cellulose nanofibers and mixing, and drying to obtain modified cellulose nanofibers; wherein the mass ratio of cellulose nanofibers to aromatic substituted oxygen-containing compounds is 100:7~9, and the mass-to-volume ratio of cellulose nanofibers to anhydrous ethanol is 1g:6mL.
[0011] As a further technical solution, the raw materials of the high-strength bio-based milk protein fiber also include 1 to 3 parts of flame retardant. The preparation method of the flame retardant includes the following steps: adding sericite and 5-bromosalicylic acid to a solvent, mixing, and drying to obtain a flame retardant.
[0012] As a further technical solution, the mass ratio of the sericite to 5-bromosalicylic acid is 70:3~5.
[0013] 5-bromosalicylic acid is mixed with sericite and added to high-strength bio-based milk protein fiber as a flame retardant. On the one hand, 5-bromosalicylic acid can form a connection with sericite through hydrogen bonds, thereby improving the dispersibility of sericite. On the other hand, the bromine element in 5-bromosalicylic acid can generate bromine free radicals at high temperatures, capture active free radicals in combustion to block the chain reaction, and promote carbonization on the surface of high-strength bio-based milk protein fiber, physically isolating heat and oxygen. 5-bromosalicylic acid and sericite as flame retardants can further enhance the flame retardant effect of the flame retardant, thereby further improving the flame retardant properties of high-strength bio-based milk protein fiber.
[0014] As a further technical solution, the cross-linking agent includes one or both of glutaraldehyde and isocyanate.
[0015] As a further technical solution, the defoaming agent is one or more of BYK-1770 defoaming agent, BYKA-530 defoaming agent or BYK-088 defoaming agent.
[0016] The present invention also provides a method for preparing high-strength bio-based milk protein fiber, comprising the following steps: S1. Dispersing bovine collagen and milk casein in water and stirring to obtain a protein solution; S2. Add the remaining components to the protein solution, mix well, and stir to obtain a spinning solution; S3. After spinning, the spinning solution is used to obtain high-strength bio-based milk protein fibers.
[0017] As a further technical solution, in step S1, during the stirring, the temperature is 30-40°C, for example, 30°C, 35°C, or 40°C; and the stirring time is 1-2h, for example, 1h, 1.5h, or 2h.
[0018] As a further technical solution, in step S2, during the stirring, the temperature is 85-95°C, for example, 86°C, 90°C, or 93°C; the stirring time is 3-5h, for example, 3.5h, 4h, or 5h.
[0019] The working principle and beneficial effects of the present invention are: The high-strength bio-based milk protein fiber prepared by the present invention is added with cellulose nanofibers modified with aromatic substituted oxygen-containing compounds, and the prepared bio-based milk protein fiber has high mechanical strength. In the prior art, in order to improve the strength of bio-based milk protein fibers, the method of adding fibers is often adopted, but the cellulose nanofibers have the problem of easy agglomeration, resulting in the effect of improving the mechanical strength of the bio-based milk protein fibers not being well achieved. The present invention, on the other hand, modifies the surface of the cellulose nanofibers by adding aromatic substituted oxygen-containing compounds, thereby improving the surface hydrophobic effect, thereby further improving the dispersibility of the cellulose nanofibers, and can further improve the mechanical strength of the high-strength bio-based milk protein fibers. DETAILED DESCRIPTION
[0020] 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.
[0021] In the following examples and comparative examples: polyvinyl alcohol, model BP-03; bovine collagen, item number 100149, purchased from Mingrui Group Co., Ltd.; bovine casein, item number RS-0516-381, purchased from Shanxi Ruisi Biotechnology Co., Ltd.; cellulose nanofibers, with a fiber width of 10~50nm and a length of 0.5~3μm, purchased from Wuhan Huaxiang Kejie Biotechnology Co., Ltd.; sericite, particle size 45μm.
[0022] Example 1 High-strength bio-based milk protein fiber, comprising the following raw materials in parts by weight: 70 parts of milk casein, 6 parts of bovine collagen, 1 part of polyvinyl alcohol, 2 parts of modified cellulose nanofibers, 1 part of glutaraldehyde, 1 part of BYK-1770 defoaming agent, 210 parts of water; The method for preparing modified cellulose nanofibers comprises the following steps: dissolving 2-benzylpropionic acid in anhydrous ethanol, adding cellulose nanofibers, mixing for 3 hours, and drying to obtain modified cellulose nanofibers; wherein the mass ratio of cellulose nanofibers to 2-benzylpropionic acid is 100:7, and the mass-to-volume ratio of cellulose nanofibers to anhydrous ethanol is 1g:6mL; The preparation method of high-strength bio-based milk protein fiber comprises the following steps: S1. Disperse bovine collagen and milk casein in water and stir at 35° C. for 1 h 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. S3. After the spinning solution is spun, high-strength bio-based milk protein fiber is obtained.
[0023] Example 2 Compared with Example 1, the only difference of Example 2 is that the high-strength bio-based milk protein fiber in this example includes the following raw materials in parts by weight: 75 parts of milk casein, 8 parts of bovine collagen, 3 parts of polyvinyl alcohol, 3 parts of modified cellulose nanofibers (the same as Example 1), 1.5 parts of glutaraldehyde, 2 parts of BYKA-530 defoaming agent, and 230 parts of water.
[0024] Example 3 Compared with Example 1, the only difference of Example 3 is that the high-strength bio-based milk protein fiber in this example includes the following raw materials in parts by weight: 80 parts of milk casein, 10 parts of bovine collagen, 5 parts of polyvinyl alcohol, 5 parts of modified cellulose nanofibers (the same as Example 1), 2.5 parts of isocyanate, 3 parts of BYK-088 defoaming agent, and 250 parts of water.
[0025] Example 4 Compared with Example 2, the only difference of Example 4 is that in this example, 2-benzylpropionic acid is replaced by an equal amount of 2-benzylpropane-1,3-diol.
[0026] Example 5 Compared with Example 2, the only difference of Example 5 is that in this example, 2-benzylpropionic acid is replaced by an equal amount of 2-(hydroxymethyl)-2-phenylpropane-1,3-diol.
[0027] Example 6 Compared with Example 4, the only difference of Example 6 is that the mass ratio of cellulose nanofibers to 2-benzylpropane-1,3-diol in this example is 25:2.
[0028] Example 7 Compared with Example 4, the only difference of Example 7 is that the mass ratio of cellulose nanofibers to 2-benzylpropane-1,3-diol in this example is 100:9.
[0029] Example 8 Compared with Example 2, the only difference of Example 8 is that the raw material of the high-strength bio-based milk protein fiber in this example further includes 2 parts of flame retardant, and the 2 parts of flame retardant are added in step S2; The preparation method of the flame retardant comprises the following steps: adding 70 parts of sericite and 4 parts of 5-bromosalicylic acid into 100 parts of ethanol, mixing for 2.5 hours, and drying to obtain the flame retardant.
[0030] Example 9 Compared with Example 8, the only difference of Example 9 is that the flame retardant in this example is only sericite.
[0031] Example 10 Compared with Example 8, the only difference in Example 10 is that 5-bromosalicylic acid is replaced by an equal amount of silane coupling agent KH560.
[0032] Comparative Example 1 Compared with Example 2, the only difference in Comparative Example 1 is that the modified cellulose nanofibers are replaced by an equal amount of cellulose nanofibers.
[0033] The high-strength bio-based milk protein fibers in Examples 1 to 10 and Comparative Example 1 were tested as follows: 1. Mechanical strength test: The breaking strength test is carried out in accordance with the standard GB / T14337-2022 "Test method for tensile properties of chemical staple fibers"; 2. Flame retardant performance test: Tested in accordance with standard FZ / T50016-2023 "Test method for combustion performance of chemical fibers - oxygen index method"; The measurement results are shown in Tables 1 and 2: Table 1 Mechanical strength test results of high-strength bio-based milk protein fiber
[0034] The data in Table 1 indicate that the high-strength bio-based milk protein fibers prepared by the present invention have high mechanical strength. Comparison of Examples 1-7 and Comparative Example 1 demonstrates that the addition of aromatically substituted oxygen-containing compound-modified cellulose nanofibers significantly improves the dry and wet breaking strength of the high-strength bio-based milk protein fibers.
[0035] Table 2 Flame retardant test results of high-strength bio-based milk protein fiber
[0036] The data in Table 2 indicate that the high-strength bio-based milk protein fiber prepared by the present invention exhibits excellent flame retardancy. Comparison of Examples 2, 8, and 10 demonstrates that the addition of a flame retardant consisting of 5-bromosalicylic acid and sericite significantly increases the oxygen index and flame retardancy of the high-strength bio-based milk protein fiber.
[0037] 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 milk protein fiber, characterized in that: The invention comprises the following raw materials in parts by weight: 70-80 parts of milk casein, 6-10 parts of bovine collagen, 1-5 parts of polyvinyl alcohol, 2-5 parts of modified cellulose nanofibers, 1-2.5 parts of a cross-linking agent, 1.5-3 parts of a defoaming agent, and 210-250 parts of water; the modified cellulose nanofibers are obtained by modifying cellulose nanofibers with an aromatic substituted oxygen-containing compound.
2. The high-strength bio-based milk protein fiber according to claim 1, characterized in that The mass ratio of the aromatic substituted oxygen-containing compound to the cellulose nanofibers in the raw materials of the modified cellulose nanofibers is 7-9:
100.
3. The high-strength bio-based milk protein fiber according to claim 1, characterized in that The aromatic substituted oxygen-containing compound includes one or more of 2-benzylpropionic acid, 2-benzylpropane-1,3-diol, and 2-(hydroxymethyl)-2-phenylpropane-1,3-diol.
4. The high-strength bio-based milk protein fiber according to claim 1, characterized in that The cellulose nanofibers have a width of 10-50 nm and a length of 0.5-3 μm.
5. The high-strength bio-based milk protein fiber according to claim 1, characterized in that: The raw materials of the high-strength bio-based milk protein fiber also include 1 to 3 parts of flame retardant; The preparation method of the flame retardant comprises the following steps: adding sericite and 5-bromosalicylic acid into a solvent, mixing, and drying to obtain the flame retardant.
6. The high-strength bio-based milk protein fiber according to claim 1, characterized in that The cross-linking agent includes one or both of glutaraldehyde and isocyanate.
7. The high-strength bio-based milk protein fiber according to claim 1, characterized in that: The deaerator is one or more of BYK-1770 deaerator, BYKA-530 deaerator or BYK-088 deaerator.
8. A method for preparing high-strength bio-based milk protein fiber, for preparing the high-strength bio-based milk protein fiber according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1. Dispersing milk casein and bovine collagen in water and stirring to obtain a protein solution; S2. Add the remaining components to the protein solution, mix well, and stir to obtain a spinning solution; S3. After spinning, the spinning solution is used to obtain high-strength bio-based milk protein fibers.
9. The method for preparing high-strength bio-based milk protein fiber according to claim 8, characterized in that: In step S1, during the stirring, the temperature is 30-40° C. and the stirring time is 1-2 h.
10. The method for preparing high-strength bio-based milk protein fiber according to claim 8, characterized in that: In step S2, during the stirring, the temperature is 85-95° C. and the stirring time is 3-5 hours.