Zein gel spinning solution with high spinnability as well as preparation method and spinning method of zein gel spinning solution
By using low-temperature pre-cooling and plasticizers when preparing zein spinning liquid, the problem of poor spinability of zein spinning liquid in the prior art is solved, and an efficient and environmentally friendly spinning process is achieved, which is suitable for industrial production.
Patent Information
- Application Number
- CN202311607378.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-11-29
- Publication Date
- 2025-05-30
AI Technical Summary
The existing high-concentration zein-soluble spinning liquid has poor spinability, resulting in complex spinning process, low efficiency, and strict conditions.
By mixing water and plasticizer well, pre-cooling at low temperature, adding zein while stirring, maintaining low temperature and continuously stirring, a high-spinable zein gel spinning liquid was prepared, and spinning was performed using low-temperature gel spinning technology.
The high spinability of high concentration zein-soluble spinning liquid is achieved, the spinning process is simplified, the cost is reduced, suitable for industrial large-scale production, and the performance of fiber is improved.
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Figure CN120060992A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of protein materials, and particularly relates to a zein gel spinning solution with high spinnability, a preparation method thereof, and a spinning method thereof. Background Art
[0002] Zein is uniformly distributed in the form of protein particles (with a diameter of about 1 μm) between the starch granules (with a diameter of 5 - 35 μm) in the cytoplasm of the maize endosperm, and is the main protein in corn gluten meal, a by-product of corn starch production. Zein is a heterogeneous mixture composed of peptides with different molecular weights, solubilities, and charges, connected by disulfide bonds. The average molecular weight is 44KDa, and more than 50% are hydrophobic amino acids, with unique solubility, such as being soluble in binary solvent blends such as ethanol / water. Due to the lack of lysine and tryptophan, its nutritional value is low, resulting in problems of resource waste and low added value.
[0003] Zein has advantages such as degradability, renewability, non-toxicity, and environmental friendliness. Its unique composition and structure endow it with amphiphilicity, self-assembly, and other properties, and it can be applied in fields such as packaging materials, biomedicine, and textile fibers. As a renewable resource, the fibers prepared from zein have good properties and unique functions, and have important research value in the textile field.
[0004] Zein fiber is a material with very high application value and development prospects, and some preliminary exploration work was carried out more than half a century ago. Zein has been applied to the textile industry, and many researchers have used methods such as wet spinning, dry spinning, and electrospinning for spinning, but the spinning solution has poor stability, low concentration, complex spinning process, low spinning efficiency, requires harsh conditions such as strong alkalinity, and the fiber properties are poor. Wet spinning is the most commonly used method, but the process is cumbersome and requires a large amount of chemical reagents. To reduce the cost of fiber preparation, gel spinning has received attention. Some researchers have tried to use a screw extruder for high-concentration (45%) zein spinning, but the spinnability of the spinning solution system is poor, and fibers have not been successfully prepared. Summary of the Invention
[0005] The purpose of the present invention is to solve the technical problem of poor spinnability of the existing high-concentration zein spinning solution, and to provide a zein gel spinning solution with high spinnability, a preparation method thereof, and a spinning method thereof.
[0006] The technical solution of the present invention:
[0007] One of the purposes of the present invention is to provide a preparation method of a zein gel spinning solution with high spinnability, and the method:
[0008] Mix water and plasticizer evenly and pre-cool at low temperature, then add zein while stirring, and keep the low temperature and continue stirring until evenly mixed to obtain a highly spinnable zein gel spinning solution.
[0009] Further defined, the plasticizer is one or more of glycerol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol.
[0010] Further defined, the low temperature refers to 0 - 4 °C.
[0011] Further defined, the concentration of water in the spinning solution is 30 - 40 wt.%.
[0012] Further defined, the concentration of plasticizer in the spinning solution is 5 - 15 wt.%.
[0013] Further defined, the concentration of zein in the spinning solution is 50 - 60 wt.%.
[0014] Further defined, stir continuously for 10 - 30 min.
[0015] The second object of the present invention is to provide a highly spinnable zein gel spinning solution prepared by the above method.
[0016] The third object of the present invention is to provide a spinning method based on the highly spinnable zein gel spinning solution, and the method:
[0017] Add the spinning solution to a screw propeller and spin using low-temperature gel spinning technology to obtain zein fibers.
[0018] Further defined, the spinning temperature is 40 - 60 °C.
[0019] Further defined, the screw speed is 800 - 1200 rpm, and the collection speed is 200 - 400 mm / min.
[0020] The beneficial effects of the present invention compared with the prior art:
[0021] (1) The zein spinning solution prepared by the present invention has a simple preparation method, mild conditions, high efficiency, environmental protection, low cost, and is suitable for large-scale industrial production.
[0022] (2) The zein spinning solution prepared by the present invention has the advantages of high concentration, good stability, mild conditions, strong spinnability, etc.; combined with the low-temperature reaction gel spinning technology of high-concentration zein, it is beneficial to achieve high-efficiency spinning. Description of the Drawings
[0023] Figure 1Spinnability change diagram of the highly spinnable zein gel spinning solution prepared in Example 5 with gradient temperature increase; wherein (A) zein is mixed with water and a plasticizer at low temperature, (B) a hydrate is formed, (C) and (D) the temperature is increased to form a uniformly viscous gel spinning solution, and (E) and (F) it can be stretched into fibrous form;
[0024] Figure 2 Zein fiber preparation process and morphology diagram of the obtained fibers in Example 9; wherein, (A) flow chart, (B) scanning electron microscope image of the fiber surface, (C) scanning electron microscope image of the fiber cross-section. Detailed implementation manners
[0025] To make the above objects, features and advantages of the present invention more obvious and understandable, the following detailed description of the specific implementation manners of the present invention will be given in conjunction with the embodiments of the specification.
[0026] Many specific details are set forth in the following description to facilitate a thorough understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Those skilled in the art can make similar generalizations without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.
[0027] Secondly, the so-called "one embodiment" or "embodiment" herein refers to a specific feature, structure or characteristic that may be included in at least one implementation manner of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment that excludes other embodiments.
[0028] The experimental methods used in the following embodiments are all conventional methods unless otherwise specified. The materials, reagents, methods and instruments used, unless otherwise specified, are all conventional materials, reagents, methods and instruments in the art, and those skilled in the art can obtain them through commercial channels.
[0029] Example 1: The preparation method of the highly spinnable zein gel spinning solution in this example is carried out according to the following steps:
[0030] (1) Weigh 66 mL of water and 24 g of polyethylene glycol 200 respectively, mix them evenly to obtain a solvent, and place it in a low-temperature pre-cooling at 0 °C.
[0031] (2) Weigh 110 g of zein, add it to the above solvent while stirring, and continue to stir on a magnetic stirrer for 20 min until evenly mixed to obtain a zein gel spinning solution with a concentration of 55% (w / w). The entire mixing and stirring process is carried out in an ice-water bath to maintain low temperature and prevent zein from sticking.
[0032] The prepared spinning solution was heated in a water bath and gradually heated to 30°C, 40°C, 50°C, 60°C, 70°C, and 80°C respectively, and stirred to form a viscous and uniform gel spinning solution. It was found that good spinning performance was obtained between 40 - 60°C.
[0033] The concentration of zein in the above spinning solution was 55% (w / w), the concentration of water was 33% (w / w), and the concentration of polyethylene glycol 200 was 12% (w / w).
[0034] Example 2: The preparation method of the highly spinnable zein gel spinning solution in this example was carried out according to the following steps:
[0035] (1) Weigh 66 mL of water and 24 g of ethylene glycol respectively, mix them evenly to obtain a solvent, and store it in a refrigerator at 0°C for pre-cooling.
[0036] (2) Weigh 110 g of zein, add it to the above solvent while stirring, and continue to stir on a magnetic stirrer for 20 min until evenly mixed to obtain a zein gel spinning solution with a concentration of 55% (w / w). The entire mixing and stirring process was carried out in an ice-water bath to maintain a low temperature and prevent the zein from sticking.
[0037] The prepared spinning solution was heated in a water bath and gradually heated to 30°C, 40°C, 50°C, 60°C, 70°C, and 80°C respectively, and stirred to form a viscous and uniform gel spinning solution. It was found that good spinning performance was obtained between 40 - 60°C.
[0038] The concentration of zein in the above spinning solution was 55% (w / w), the concentration of water was 33% (w / w), and the concentration of ethylene glycol was 12% (w / w).
[0039] Example 3: The preparation method of the highly spinnable zein gel spinning solution in this example was carried out according to the following steps:
[0040] (1) Weigh 66 mL of water and 24 g of 1,2 - propanediol respectively, mix them evenly to obtain a solvent, and store it in a refrigerator at 0°C for pre-cooling.
[0041] (2) Weigh 110 g of zein, add it to the above solvent while stirring, and continue to stir on a magnetic stirrer for 20 min until evenly mixed to obtain a zein gel spinning solution with a concentration of 55% (w / w). The entire mixing and stirring process was carried out in an ice-water bath to maintain a low temperature and prevent the zein from sticking.
[0042] The prepared spinning solution was heated in a water bath and gradually heated to 30°C, 40°C, 50°C, 60°C, 70°C, and 80°C respectively, and stirred to observe the phenomenon. At 60°C, it could be stretched into fine filaments and had good spinnability.
[0043] The concentration of zein in the above spinning solution is 55% (w / w), the concentration of water is 33% (w / w), and the concentration of 1,2 - propanediol is 12% (w / w).
[0044] Example 4: The preparation method of the highly spinnable zein gel spinning solution in this example is carried out according to the following steps:
[0045] (1) Weigh 72 mL of water and 18 g of 1,3 - propanediol separately, mix them evenly to obtain a solvent, and store it in a refrigerator at 0 °C for pre - cooling.
[0046] (2) Weigh 110 g of zein, add it to the above - mentioned solvent while stirring, and continue to stir on a magnetic stirrer for 20 min until it is evenly mixed to obtain a zein gel spinning solution with a concentration of 55% (w / w). The entire mixing and stirring process is carried out in an ice - water bath to keep it at a low temperature and prevent the zein from sticking.
[0047] Heat the prepared spinning solution in a water bath, and gradually heat it to 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C respectively, and stir to observe the phenomenon. It can be stretched into fine filaments at about 60 °C, and the spinnability is good.
[0048] The concentration of zein in the above spinning solution is 55% (w / w), the concentration of water is 36% (w / w), and the concentration of 1,3 - propanediol is 9% (w / w).
[0049] Example 5: The preparation method of the highly spinnable zein gel spinning solution in this example is carried out according to the following steps:
[0050] (1) Weigh 66 mL of water and 24 g of 1,3 - propanediol separately, mix them evenly to obtain a solvent, and store it in a refrigerator at 0 °C for pre - cooling.
[0051] (2) Weigh 110 g of zein, add it to the above - mentioned solvent while stirring, and continue to stir on a magnetic stirrer for 20 min until it is evenly mixed to obtain a zein gel spinning solution with a concentration of 55% (w / w). The entire mixing and stirring process is carried out in an ice - water bath to keep it at a low temperature and prevent the zein from sticking.
[0052] Heat the prepared spinning solution in a water bath, and gradually heat it to 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C respectively, and stir to observe the phenomenon. The spinnability change diagram is as Figure 1 shown. It can be seen that it can be stretched into fine filaments at 55 - 60 °C, and the spinnability is good.
[0053] The concentration of zein in the above spinning solution is 55% (w / w), the concentration of water is 33% (w / w), and the concentration of 1,3-propanediol is 12% (w / w).
[0054] Example 6: The preparation method of the highly spinnable zein gel spinning solution in this example is carried out according to the following steps:
[0055] (1) Weigh 78 mL of water and 12 g of 1,4-butanediol respectively, mix them evenly to obtain a solvent, and store it in a refrigerator at 0 °C for pre-cooling.
[0056] (2) Weigh 110 g of zein, add it to the above solvent while stirring, and continue to stir on a magnetic stirrer for 20 min until evenly mixed to obtain a zein gel spinning solution with a concentration of 55% (w / w). The entire mixing and stirring process is carried out in an ice-water bath to maintain a low temperature and prevent the zein from sticking.
[0057] Heat the prepared spinning solution in a water bath, and gradually heat it to 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, and 80 °C respectively, and stir to observe the phenomenon. It can be stretched into fine filaments at 45 - 55 °C, and the spinnability is good.
[0058] The concentration of zein in the above spinning solution is 55% (w / w), the concentration of water is 39% (w / w), and the concentration of 1,4-butanediol is 6% (w / w).
[0059] Example 7: The preparation method of the highly spinnable zein gel spinning solution in this example is carried out according to the following steps:
[0060] (1) Weigh 72 mL of water and 18 g of 1,4-butanediol respectively, mix them evenly to obtain a solvent, and store it in a refrigerator at 0 °C for pre-cooling.
[0061] (2) Weigh 110 g of zein, add it to the above solvent while stirring, and continue to stir on a magnetic stirrer for 20 min until evenly mixed to obtain a zein gel spinning solution with a concentration of 55% (w / w). The entire mixing and stirring process is carried out in an ice-water bath to maintain a low temperature and prevent the zein from sticking.
[0062] Heat the prepared spinning solution in a water bath, and gradually heat it to 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, and 80 °C respectively, and stir to observe the phenomenon. It can be stretched into fine filaments at 45 - 55 °C, and the spinnability is good.
[0063] The concentration of zein in the above spinning solution is 55% (w / w), the concentration of water is 36% (w / w), and the concentration of 1,4-butanediol is 9% (w / w).
[0064] Example 8: The preparation method of the highly spinnable zein gel spinning solution in this example is carried out according to the following steps:
[0065] (1) Weigh 66 mL of water and 24 g of 1,4-butanediol respectively, mix them evenly to obtain a solvent, and store it in a refrigerator at 0 °C for pre-cooling.
[0066] (2) Weigh 110 g of zein, add it to the above solvent while stirring, and continue to stir on a magnetic stirrer for 20 min until evenly mixed to obtain a zein gel spinning solution with a concentration of 55% (w / w). The entire mixing and stirring process is carried out in an ice-water bath to maintain a low temperature and prevent the zein from sticking.
[0067] Heat the prepared spinning solution in a water bath, and gradually heat it to 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, and 80 °C respectively, and stir to observe the phenomenon. It can be stretched into fine filaments at 40 - 55 °C, and the spinnability is good.
[0068] In the above spinning solution, the concentration of zein is 55% (w / w), the concentration of water is 33% (w / w), and the concentration of 1,4-butanediol is 12% (w / w).
[0069] The high-concentration zein spinning solution prepared through the above examples has good stability and spinnability.
[0070] Example 9: The preparation method of the fiber based on the highly spinnable zein gel spinning solution in this example is carried out according to the following steps:
[0071] (1) Weigh 66 mL of water and 18 g of 1,4-butanediol respectively, mix them evenly to obtain a solvent, and store it in a refrigerator at 0 °C for pre-cooling.
[0072] (2) Weigh 110 g of zein, add it to the above solvent while stirring, and continue to stir on a magnetic stirrer for 20 min until evenly mixed to obtain a zein gel spinning solution with a concentration of 55% (w / w). The entire mixing and stirring process is carried out in an ice-water bath to maintain a low temperature and prevent the zein from sticking.
[0073] In the above spinning solution, the concentration of zein is 56.7% (w / w), the concentration of water is 34% (w / w), and the concentration of 1,4-butanediol is 9.3% (w / w).
[0074] (3) Add the above spinning solution to the feed port of the screw extruder, and push it to the heating chamber through the screw extruder. Keep the temperature at 50 °C, the rotation speed of the screw extruder is 1000 rpm, and the speed of the fiber winding machine is 300 mm / min to obtain zein fibers.
[0075] The gel spinning process and the morphology of the prepared fibers are as follows Figure 2 As shown, it can be found that the fibers prepared by this method have a dense structure and a relatively uniform appearance, indicating that the gel spinning solution prepared by the inventive method has high spinnability.
[0076] The mechanical properties of the fibers were tested according to GB / T 14463-2022, and the results are shown in Table 1.
[0077] Table 1 Mechanical properties of the fibers
[0078]
[0079] The breaking strength of the fibers prepared by the above method reached 5.82±1.86 cN / dtex.
[0080] Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Anyone familiar with this technology can make various modifications and decorations without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be defined by the claims.
Claims
1. A preparation method of a highly spinnable zein gel spinning solution, characterized in that, the method: Mix water and a plasticizer and pre-cool at a low temperature, then add zein while stirring, and keep the low temperature and continuously stir until evenly mixed to obtain a highly spinnable zein gel spinning solution.
2. The method according to claim 1, characterized in that, the plasticizer is one or several of glycerol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol.
3. The method according to claim 1, characterized in that, the low temperature refers to 0 - 4 °C.
4. The method according to claim 1, characterized in that, the concentration of water in the spinning solution is 30 - 40 wt.%, the concentration of the plasticizer is 5 - 15 wt.%, and the concentration of zein is 50 - 60 wt.%.
5. The method according to claim 1, characterized in that, continuously stir for 10 - 30 min.
6. A highly spinnable zein gel spinning solution prepared by the method according to any one of claims 1 - 5.
7. A spinning method based on the highly spinnable zein gel spinning solution according to claim 6, characterized in that, the method: Add the spinning solution to a screw propeller and carry out spinning by using a low-temperature gel spinning technique to obtain zein fibers.
8. The method according to claim 7, characterized in that, the spinning temperature is 40 - 60 °C.
9. The method according to claim 7, characterized in that, the screw rotation speed is 800 - 1200 rpm.
10. The method according to claim 7, characterized in that, the collection speed is 200 - 400 mm / min.