Preparation method for protein composite fiber

Abstract

The present invention relates to the field of fibers, and in particular, to a preparation method for a protein composite fiber. The preparation method comprises spinning, pretreatment, surface treatment, preparation of modified mineral powder, loading, mixing and crosslinking. A pretreated nascent fiber is immersed in a protein composite solution to be in full contact with modified extract mineral powder and a soluble protein, and a crosslinking reaction is carried out; the structure of the dried fiber is more compact; the extract and the soluble protein are more stable in the fiber while the fiber strength is improved; and the loss rate is less than 1% after washing for 50 times. The protein composite fiber prepared by the present invention is skin-friendly and soft, has good moisture absorption and moisturizing effects, and is rich in amino acid and protein, wherein the content of the protein is up to about 12%. Moreover, in the present invention, a common fiber is used as a base material, thereby achieving natural antibacterial, anti-oxidation and deodorizing effects while endowing fibers such as viscose, acrylic fibers, polyester, chinlon, vinylon, and polypropylene fibers with the advantages of a natural protein on the basis of ensuring excellent properties of the base material itself, and thus the range of application is wider.

Description

A method for preparing protein composite fiber Technical Field

[0001] The invention belongs to the technical field of fiber spinning, and particularly relates to a method for preparing protein composite fibers. Background Art

[0002] Natural protein fibers such as wool and silk contain a special scale structure composed of amino acids, so they have good warmth retention, moisture absorption and elasticity, and are loved by many consumers. However, the sources of natural protein fibers are limited, and their applications are restricted. Modification of natural protein fibers has become one of the hot topics in the textile field.

[0003] Protein modified fibers are mostly milk protein fibers, soybean protein fibers, feather protein fibers, collagen fibers, silkworm pupa protein fibers, wool keratin fibers, etc. The above proteins are mostly based on polyvinyl alcohol, polyacrylonitrile or viscose fibers. For example, in the patent No. "CN202110312949.5" entitled "A flexible silk fibroin / polyvinyl alcohol composite fiber and its preparation method", a silk fibroin aqueous solution and a polyvinyl alcohol aqueous solution are blended, and the ratio of silk fibroin to polyvinyl alcohol is adjusted to select a ratio with relatively stable compatibility to prepare a silk fibroin / polyvinyl alcohol composite spinning aqueous solution; dry-jet wet spinning technology is used to prepare silk fibroin / polyvinyl alcohol composite fibers; in the patent No. "CN201310356755.0" entitled "A method for preparing polyacrylonitrile fiber with protein as a modifier", ionic liquid is used as a solvent, and a uniform mixing method is adopted to prepare protein-modified polypropylene. A homogeneous spinning solution of acrylonitrile is prepared by dry-jet wet spinning technology with water as a coagulant to prepare protein-modified polyacrylonitrile fiber; in the patent number "CN201210033741.0" entitled "A production process for wool protein composite viscose fiber", wool protein is dissolved in a sodium hydroxide aqueous solution to prepare a wool protein solution, which is mixed with a viscose spinning solution and then spun to prepare wool protein composite viscose fiber; in the patent number "CN201210304021.3" entitled "A method for preparing a pupa protein cellulose composite viscose filament", pupa protein powder is dissolved in a sodium hydroxide aqueous solution, filtered, and then a protein denaturing agent is added to obtain a pupa protein spinning solution, which is mixed with the viscose spinning solution and spun to prepare a pupa protein cellulose composite viscose filament.

[0004] Adding protein to fibers can certainly make them softer and more skin-friendly, but protein is expensive and unstable in nature. It is greatly affected by acidity, alkali, high temperature, etc., has a single function, and a narrow range of use. Therefore, developing a protein composite fiber with no usage limitations and complete functions can meet customers' growing consumption needs. Summary of the Invention

[0005] To solve the problems existing in the prior art, the present invention provides a method for preparing protein composite fibers to achieve the following invention objectives:

[0006] 1. Avoid the impact of protein powder on the mechanical properties of the fiber;

[0007] 2. Prevent protein powder from affecting the spinnability of fiber spinning solution, increasing spinning difficulty and production costs;

[0008] 3. Increase the protein content in the fiber and improve the fiber's washability; at the same time, the protein composite material in the fiber can give the fiber more functionality.

[0009] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0010] A method for preparing a protein composite fiber, comprising the following steps:

[0011] S1. Spinning

[0012] The fiber spinning raw materials are wet-spun or melt-spun to obtain spun fibers with a fineness of 0.5 to 10 dtex.

[0013] Preferably, the fiber spinning raw material is one of viscose spinning solution, acrylic spinning solution, polyester, nylon, vinylon spinning solution, and polypropylene.

[0014] S2. Preprocessing

[0015] The spun fibers are hydrolyzed to obtain pretreated spun fibers.

[0016] S3. Surface treatment

[0017] The mineral powder is added to deionized water and ultrasonically dispersed for 2 to 5 minutes, an epoxy silane coupling agent is added and stirred for 10 to 15 minutes, the pH is adjusted to 8 to 10, and the temperature is raised to 60 to 70° C. to react for 30 to 40 minutes to graft epoxy groups on the surface of the mineral powder. After the reaction is completed, the mineral powder is centrifuged, filtered, washed, and naturally dried to obtain the surface-treated mineral powder.

[0018] Preferably, the mineral powder is one or more of zeolite, medical stone, quartz stone, montmorillonite, sepiolite, and bentonite, and has a particle size of 1 to 2 μm.

[0019] Preferably, the mass ratio of the mineral powder to deionized water is 1:6-8.

[0020] Preferably, the epoxysilane coupling agent is one or more of 3-(2,3-epoxypropyloxy)propylmethyldimethoxysilane, 3-(2,3-epoxypropyloxy)propylmethyldiethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and the added amount is 25-35% of the mass of the mineral powder.

[0021] Preferably, the frequency of the ultrasonic dispersion is 20 to 30 kHz, and the stirring rate is 500 to 600 r / min.

[0022] Preferably, the centrifugal speed is 3000-4000 r / min, and the washing method uses anhydrous ethanol.

[0023] S4. Preparation of modified mineral powder

[0024] The surface-treated mineral powder is added to deionized water and stirred for 15 to 30 minutes. The catalyst is added and stirred for 1 to 2 minutes, and then 1,2-propylene glycol and sodium hydroxide solution are added. The temperature is raised to 50 to 60° C. and stirred for 2 to 3 hours. Then diethylenetriamine is added and stirred for 90 to 120 minutes. After the reaction is completed, the mixture is cooled to room temperature, centrifuged, filtered, washed, and dried to obtain the modified mineral powder.

[0025] Preferably, the mass ratio of the surface-treated mineral powder to deionized water is 1:4-6.

[0026] Preferably, the catalyst is one or more of BF3 and SnCl4, and the added amount is 1 to 1.5% of the mass of the surface-treated mineral powder.

[0027] Preferably, the amount of 1,2-propylene glycol added is 13-17% of the mass of the surface-treated mineral powder; the concentration of the sodium hydroxide solution is 4-8 mol / L, and the amount added is 30-40% of the mass of the surface-treated mineral powder; the amount of diethylenetriamine added is 18-24% of the mass of the surface-treated mineral powder.

[0028] Preferably, the stirring rate is 500-600 r / min; the centrifugal rate is 3000-4000 r / min; the washing adopts an ethanol solution with a mass fraction of 85-92%; the drying temperature is 50-60°C and the time is 4-6 hours.

[0029] S5, load

[0030] The plant extract is added to deionized water and stirred for 10 to 20 minutes to obtain a plant extract solution, and then the modified mineral powder is added to the plant extract solution and stirred at 30 to 40° C. for 30 to 50 minutes, and then dried to obtain the modified extract mineral powder.

[0031] Preferably, the plant extract is one or more of pteris viridis extract, purslane extract, aloe vera extract, wormwood extract, ginger extract, mint extract, camellia extract, marigold extract, isatis indigotica extract, and sarcandra extract, and the particle size is 100-200 nm.

[0032] Preferably, the mass ratio of the plant extract to deionized water is 1:4-7.

[0033] Preferably, the added amount of the modified mineral powder is 15-18% of the mass of the plant extract.

[0034] Preferably, the stirring rate is 200-300 r / min, the drying temperature is 50-60° C., and the drying time is 4-6 h.

[0035] S6, Hybrid

[0036] Add the modified extract mineral powder and soluble protein into deionized water and stir for 10 to 20 minutes to obtain a protein complex solution.

[0037] Preferably, the mass ratio of the modified extract mineral powder, soluble protein powder and deionized water is 20-30:13-18:100-110.

[0038] Preferably, the soluble protein is one or more of cashmere protein, oat protein, milk protein, collagen, soy protein, silk fibroin, feather protein, quinoa protein, silkworm pupa protein, pearl protein, keratin, silk protein, corn protein, peanut protein, casein, goat milk protein, polygonatum protein, poria protein, aloe protein, phycocyanin, whey protein, peptide protein, pea protein, and wheat germ protein, with a particle size of 2 to 4 μm.

[0039] Preferably, the stirring rate is 400-500 r / min.

[0040] S7, cross-linking

[0041] The nascent fiber is immersed in the protein composite liquid, heated to 130-150° C. and reacted for 10-30 minutes, and then washed, dried and oiled to obtain the protein composite fiber.

[0042] Preferably, the drying temperature is 80-90° C. and the drying time is 2-4 hours; the oiling agent used in the oiling is one of JL-DY, TK-1259 and the like.

[0043] Due to the adoption of the above technical solution, the technical effects achieved by the present invention are:

[0044] 1. The protein composite fiber prepared by the present invention is skin-friendly and soft, has good moisture absorption and moisturizing effects, has a smooth fiber surface, and is rich in amino acids and proteins, of which the protein content is as high as about 12%; and the present invention uses commonly used fibers as the base material, ensuring the excellent properties of the base material itself, while giving the advantages of natural protein fibers to viscose, acrylic, polyester, nylon, vinylon, polypropylene and other fibers. Compared with pure natural protein fibers, it has a broader consumer market and application range, especially in the field of medical textiles.

[0045] 2. The protein composite fiber prepared by the present invention has excellent antibacterial effect. After washing 50 times, the antibacterial rate against Staphylococcus aureus is greater than 98%, the antibacterial rate against Escherichia coli is greater than 97%, and the antibacterial rate against Candida albicans is greater than 96% (determined in accordance with GB / T 20944.3-2008).

[0046] 3. The protein composite fiber prepared by the present invention has an antioxidant effect, and the DPPH free radical scavenging rate is greater than 75% (tested in accordance with T / CCTA 20102-2023). At the same time, due to the enhanced hygroscopicity of the fiber, the antistatic effect is improved.

[0047] 4. The protein composite fiber prepared by the present invention has excellent moisturizing effect. Taking aloe vera protein as an example, 30% protein composite fiber and 70% polyester are made into fabrics. The fabric absorbs moisture for 5 hours at 20°C and 80% RH, and the moisture absorption rate is measured to be greater than 4%. It also has a good deodorizing effect, with the removal rates of ammonia, acetic acid, and isovaleric acid all reaching more than 90% (determined in accordance with GB / T 33610.3-2019).

[0048] 5. The present invention treats the surface of mineral powder to graft epoxy groups, then reacts it with polyol, sodium hydroxide, and diethylenetriamine to produce a modified mineral powder grafted with epoxy compounds. Due to the grafting of amino and epoxy groups, the modified mineral powder exhibits excellent dispersibility and adsorption properties, with the loading rate of the modified extract mineral powder exceeding 80%.

[0049] 6. After the primary fiber is hydrolyzed, the internal structure of the fiber becomes loose from dense. It is immersed in the protein composite liquid and fully contacted with the modified extract mineral powder and soluble protein. Under the condition of 130-150°C, the epoxy groups in the modified extract mineral powder open the ring and produce cross-linking reactions with the soluble protein and fiber, forming a protein composite material on the surface and inside of the fiber. After drying, the fiber structure becomes denser, the fiber strength is improved, and the plant extract and soluble protein are more stable in the fiber. After washing 50 times, the loss rate is less than 1%. In addition, no other aldehyde cross-linking agents are required during the cross-linking process. The fiber does not contain formaldehyde, heavy metals and other substances harmful to the body, making it more environmentally friendly and safe. DETAILED DESCRIPTION

[0050] The present invention will be further described below with reference to specific embodiments. Example

[0051] A method for preparing a protein composite fiber, comprising the following steps:

[0052] S1. Spinning

[0053] The viscose spinning solution was wet-spun to obtain nascent fibers with a fineness of 3.5 dtex.

[0054] S2. Preprocessing

[0055] The as-spun fibers were immersed in a 0.5% by mass sulfuric acid solution and hydrolyzed at 70°C for 20 minutes to obtain pretreated as-spun fibers.

[0056] S3. Surface treatment

[0057] The mineral powder was added to deionized water and ultrasonically dispersed for 4 minutes. An epoxy silane coupling agent was added and stirred for 12 minutes. The pH was adjusted to 9 and the temperature was raised to 65°C for reaction for 35 minutes to graft epoxy groups on the surface of the mineral powder. After the reaction was completed, the mineral powder was centrifuged, filtered, washed and naturally dried to obtain the surface-treated mineral powder.

[0058] The mineral powder is bentonite with a particle size of 1.2 μm and a specific surface area of ​​2.6 m² / g.

[0059] The mass ratio of the mineral powder to deionized water is 1:7.

[0060] The epoxysilane coupling agent is 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, and the added amount is 30% of the mass of the mineral powder.

[0061] The frequency of the ultrasonic dispersion was 25 kHz, and the stirring rate was 550 r / min.

[0062] The centrifugal speed is 3500 r / min, and the washing is performed using anhydrous ethanol.

[0063] S4. Preparation of modified mineral powder

[0064] The surface-treated mineral powder was added to deionized water and stirred for 20 minutes. The catalyst was added and stirred for 2 minutes, and then 1,2-propylene glycol and sodium hydroxide solution were added. The temperature was raised to 57°C and stirred for 2.5 hours. Diethylenetriamine was added and stirred for 110 minutes. After the reaction was completed, the mixture was cooled to room temperature, centrifuged, filtered, washed, and dried to obtain the modified mineral powder.

[0065] The mass ratio of the surface-treated mineral powder to deionized water is 1:5.

[0066] The catalyst is BF3, and the added amount is 1.2% of the mass of the surface-treated mineral powder.

[0067] The amount of 1,2-propylene glycol added is 15% of the mass of the surface-treated mineral powder; the concentration of the sodium hydroxide solution is 6 mol / L, and the amount added is 35% of the mass of the surface-treated mineral powder; the amount of diethylenetriamine added is 22% of the mass of the surface-treated mineral powder.

[0068] The stirring rate is 550 r / min; the centrifugal rate is 3500 r / min; the washing adopts an ethanol solution with a mass fraction of 90%; the drying temperature is 55° C. and the drying time is 5 hours.

[0069] S5, load

[0070] The plant extract was added to deionized water and stirred for 15 minutes to obtain a plant extract solution. The modified mineral powder was then added to the plant extract solution and stirred at 35° C. for 40 minutes. After drying, the modified extract mineral powder was obtained, and the loading rate was 86%.

[0071] The plant extracts include pteris viridis extract, purslane extract, aloe vera extract and wormwood extract in a mass ratio of 1:1:1:1, and have a particle size of 150 nm.

[0072] The mass ratio of the plant extract to deionized water is 1:5.

[0073] The added amount of the modified mineral powder is 16% of the mass of the plant extract.

[0074] The stirring rate is 250 r / min, the drying temperature is 55° C., and the drying time is 5 h.

[0075] S6, Hybrid

[0076] The modified extract mineral powder and soluble protein were added into deionized water and stirred for 15 minutes to obtain a protein complex solution.

[0077] The mass ratio of the modified extract mineral powder, soluble protein micropowder and deionized water is 25:15:105.

[0078] The soluble protein is milk protein, and the particle size is 2 μm.

[0079] The stirring rate is 450 r / min.

[0080] S7, cross-linking

[0081] The nascent fiber is immersed in the protein composite liquid, heated to 140°C for reaction for 20 minutes, and then washed, dried and oiled to obtain the protein composite fiber.

[0082] The drying temperature is 85° C. and the drying time is 3 hours; the oiling agent used in the oiling is JL-DY.

[0083] The protein composite fiber prepared in Example 1 has a dry strength of 2.92 cN / dtex, a wet strength of 2.15 cN / dtex, a fiber regain of 15.4%, a protein content of 12.6%, an antibacterial rate against Staphylococcus aureus of 98.8%, an antibacterial rate against Escherichia coli of 97.5%, and an antibacterial rate against Candida albicans of 96.7% after washing 50 times. The DPPH free radical scavenging rate is 79%, the ammonia removal rate is 98.7%, the acetic acid removal rate is 95.2%, and the isovaleric acid removal rate is 94.6%. After washing 50 times, the average loss rate of plant extracts and proteins is 0.74%. Example

[0084] A method for preparing a protein composite fiber, comprising the following steps:

[0085] S1. Spinning

[0086] The viscose spinning solution is wet-spun to obtain nascent fibers with a fineness of 2 dtex.

[0087] S2. Preprocessing

[0088] The as-spun fibers were immersed in a 0.5% by mass sulfuric acid solution and hydrolyzed at 70°C for 20 minutes to obtain pretreated as-spun fibers.

[0089] S3. Surface treatment

[0090] The mineral powder was added to deionized water and ultrasonically dispersed for 2 minutes. An epoxy silane coupling agent was added and stirred for 10 minutes. The pH was adjusted to 8 and the temperature was raised to 60°C for reaction for 30 minutes to graft epoxy groups on the surface of the mineral powder. After the reaction was completed, the mineral powder was centrifuged, filtered, washed and naturally dried to obtain the surface-treated mineral powder.

[0091] The mineral powder is bentonite with a particle size of 1 μm and a specific surface area of ​​2.3 m² / g.

[0092] The mass ratio of the mineral powder to deionized water is 1:6.

[0093] The epoxysilane coupling agent is 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane, and the added amount is 25% of the mass of the mineral powder.

[0094] The frequency of the ultrasonic dispersion was 20 kHz, and the stirring rate was 500 r / min.

[0095] The centrifugal speed is 3000 r / min, and the washing adopts anhydrous ethanol.

[0096] S4. Preparation of modified mineral powder

[0097] The surface-treated mineral powder was added to deionized water and stirred for 15 minutes. The catalyst was added and stirred for 1 minute, and then 1,2-propylene glycol and sodium hydroxide solution were added. The temperature was raised to 50°C and stirred for 2 hours. Diethylenetriamine was added and stirred for 90 minutes. After the reaction was completed, the mixture was cooled to room temperature, centrifuged, filtered, washed, and dried to obtain the modified mineral powder.

[0098] The mass ratio of the surface-treated mineral powder to deionized water is 1:4.

[0099] The catalyst is BF3, and the added amount is 1% of the mass of the surface-treated mineral powder.

[0100] The amount of 1,2-propylene glycol added is 13% of the mass of the surface-treated mineral powder; the concentration of the sodium hydroxide solution is 4 mol / L, and the amount added is 30% of the mass of the surface-treated mineral powder; the amount of diethylenetriamine added is 18% of the mass of the surface-treated mineral powder.

[0101] The stirring rate is 500 r / min; the centrifugal rate is 3000 r / min; the washing adopts an ethanol solution with a mass fraction of 85%; the drying temperature is 50° C. and the drying time is 4 hours.

[0102] S5, load

[0103] The plant extract was added to deionized water and stirred for 10 minutes to obtain a plant extract solution. The modified mineral powder was then added to the plant extract solution and stirred at 30° C. for 30 minutes. After drying, the modified extract mineral powder was obtained, and the loading rate was 82%.

[0104] The plant extracts are ginger extract, mint extract, camellia extract and marigold extract in a mass ratio of 1:1:1:1, and have a particle size of 200 nm.

[0105] The mass ratio of the plant extract to deionized water is 1:7.

[0106] The added amount of the modified mineral powder is 15% of the mass of the plant extract.

[0107] The stirring rate is 200 r / min, the drying temperature is 50° C., and the drying time is 4 h.

[0108] S6, Hybrid

[0109] The modified extract mineral powder and soluble protein were added into deionized water and stirred for 10 minutes to obtain a protein complex solution.

[0110] The mass ratio of the modified extract mineral powder, soluble protein powder and deionized water is 20:13:100.

[0111] The soluble protein is collagen, and the particle size is 4 μm.

[0112] The stirring rate is 400 r / min.

[0113] S7, cross-linking

[0114] The nascent fiber is immersed in the protein composite liquid, heated to 130°C for reaction for 10 minutes, and then washed, dried and oiled to obtain the protein composite fiber.

[0115] The drying temperature is 80° C. and the drying time is 2 h. The oiling agent used in the oiling is JL-DY.

[0116] The protein composite fiber prepared in Example 2 has a dry strength of 2.83 cN / dtex, a wet strength of 2.04 cN / dtex, a fiber regain of 14.8%, a protein content of 12.2%, an antibacterial rate against Staphylococcus aureus of 98.3%, an antibacterial rate against Escherichia coli of 97%, and an antibacterial rate against Candida albicans of 96.2% after washing 50 times. The DPPH free radical scavenging rate is 75%, the ammonia removal rate is 97.9%, the acetic acid removal rate is 94.5%, and the isovaleric acid removal rate is 94%. After washing 50 times, the average loss rate of plant extracts and proteins is 0.89%. Example

[0117] A method for preparing a protein composite fiber, comprising the following steps:

[0118] S1. Spinning

[0119] The viscose spinning solution is wet-spun to obtain nascent fibers with a fineness of 5 dtex.

[0120] S2. Preprocessing

[0121] The as-spun fibers were immersed in a 0.5% by mass sulfuric acid solution and hydrolyzed at 70°C for 20 minutes to obtain pretreated as-spun fibers.

[0122] S3. Surface treatment

[0123] The mineral powder was added to deionized water and ultrasonically dispersed for 5 minutes. An epoxy silane coupling agent was added and stirred for 15 minutes. The pH was adjusted to 10 and the temperature was raised to 70°C for reaction for 40 minutes to graft epoxy groups on the surface of the mineral powder. After the reaction was completed, the mineral powder was centrifuged, filtered, washed and naturally dried to obtain the surface-treated mineral powder.

[0124] The mineral powder is bentonite with a particle size of 2 μm and a specific surface area of ​​3 m² / g.

[0125] The mass ratio of the mineral powder to deionized water is 1:8.

[0126] The epoxysilane coupling agent is 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, and the added amount is 35% of the mass of the mineral powder.

[0127] The frequency of the ultrasonic dispersion was 30 kHz, and the stirring rate was 600 r / min.

[0128] The centrifugal speed is 4000 r / min, and the washing is performed using anhydrous ethanol.

[0129] S4. Preparation of modified mineral powder

[0130] The surface-treated mineral powder was added to deionized water and stirred for 30 minutes. The catalyst was added and stirred for 2 minutes, and then 1,2-propylene glycol and sodium hydroxide solution were added. The temperature was raised to 60°C and stirred for 3 hours. Diethylenetriamine was added and stirred for 120 minutes. After the reaction was completed, the mixture was cooled to room temperature, centrifuged, filtered, washed, and dried to obtain the modified mineral powder.

[0131] The mass ratio of the surface-treated mineral powder to deionized water is 1:6.

[0132] The catalyst is SnCl4, and the added amount is 1.5% of the mass of the surface-treated mineral powder.

[0133] The amount of 1,2-propylene glycol added is 17% of the mass of the surface-treated mineral powder; the concentration of the sodium hydroxide solution is 8 mol / L, and the amount added is 40% of the mass of the surface-treated mineral powder; the amount of diethylenetriamine added is 24% of the mass of the surface-treated mineral powder.

[0134] The stirring rate is 600 r / min; the centrifugal rate is 4000 r / min; the washing adopts an ethanol solution with a mass fraction of 92%; the drying temperature is 60° C. and the drying time is 6 hours.

[0135] S5, load

[0136] The plant extract was added to deionized water and stirred for 20 minutes to obtain a plant extract solution. The modified mineral powder was then added to the plant extract solution and stirred at 40° C. for 50 minutes. After drying, the modified extract mineral powder was obtained, and the loading rate was 85%.

[0137] The plant extracts are pteris viridis extract, aloe vera extract, isatis indigotica extract and sarcandra glabra extract in a mass ratio of 1:1; 1:1d, and have a particle size of 100 nm.

[0138] The mass ratio of the plant extract to deionized water is 1:4.

[0139] The added amount of the modified mineral powder is 18% of the mass of the plant extract.

[0140] The stirring rate is 300 r / min, the drying temperature is 60° C., and the drying time is 6 h.

[0141] S6, Hybrid

[0142] The modified extract mineral powder and soluble protein were added into deionized water and stirred for 20 minutes to obtain a protein complex solution.

[0143] The mass ratio of the modified extract mineral powder, soluble protein micropowder and deionized water is 30:18:110.

[0144] The soluble protein is soybean protein, and the particle size is 3 μm.

[0145] The stirring rate is 500 r / min.

[0146] S7, cross-linking

[0147] The nascent fiber is immersed in the protein composite liquid, heated to 150°C for reaction for 30 minutes, and then washed, dried and oiled to obtain the protein composite fiber.

[0148] The drying temperature is 90° C. and the drying time is 4 hours; the oiling agent used in the oiling is JL-DY.

[0149] The protein composite fiber prepared in Example 3 has a dry strength of 2.89 cN / dtex, a wet strength of 2.11 cN / dtex, a fiber regain of 16%, a protein content of 13.4%, an antibacterial rate against Staphylococcus aureus of 99.3%, an antibacterial rate against Escherichia coli of 98.2%, and an antibacterial rate against Candida albicans of 97.1% after washing 50 times, a DPPH free radical scavenging rate of 82%, an ammonia removal rate of 99.2%, an acetic acid removal rate of 95.6%, and an isovaleric acid removal rate of 94.9%. After washing 50 times, the average loss rate of plant extracts and proteins was 0.77%. Example

[0150] A method for preparing a protein composite fiber, comprising the following steps:

[0151] S1. Spinning

[0152] The polyester chips were melt-spun to obtain primary fibers with a fineness of 3.5 dtex.

[0153] S2. Preprocessing

[0154] The as-spun fibers were immersed in a 2% by mass sodium hydroxide solution and hydrolyzed at 80° C. for 20 min to obtain pretreated as-spun fibers.

[0155] S3. Surface treatment

[0156] The mineral powder was added to deionized water and ultrasonically dispersed for 4 minutes. An epoxy silane coupling agent was added and stirred for 12 minutes. The pH was adjusted to 9 and the temperature was raised to 65°C for reaction for 35 minutes to graft epoxy groups on the surface of the mineral powder. After the reaction was completed, the mineral powder was centrifuged, filtered, washed and naturally dried to obtain the surface-treated mineral powder.

[0157] The mineral powder is bentonite with a particle size of 1.2 μm and a specific surface area of ​​2.6 m² / g.

[0158] The mass ratio of the mineral powder to deionized water is 1:7.

[0159] The epoxysilane coupling agent is 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, and the added amount is 30% of the mass of the mineral powder.

[0160] The frequency of the ultrasonic dispersion was 25 kHz, and the stirring rate was 550 r / min.

[0161] The centrifugal speed is 3500 r / min, and the washing is performed using anhydrous ethanol.

[0162] S4. Preparation of modified mineral powder

[0163] The surface-treated mineral powder was added to deionized water and stirred for 20 minutes. The catalyst was added and stirred for 2 minutes, and then 1,2-propylene glycol and sodium hydroxide solution were added. The temperature was raised to 57°C and stirred for 2.5 hours. Diethylenetriamine was added and stirred for 110 minutes. After the reaction was completed, the mixture was cooled to room temperature, centrifuged, filtered, washed, and dried to obtain the modified mineral powder.

[0164] The mass ratio of the surface-treated mineral powder to deionized water is 1:5.

[0165] The catalyst is BF3, and the added amount is 1.2% of the mass of the surface-treated mineral powder.

[0166] The amount of 1,2-propylene glycol added is 15% of the mass of the surface-treated mineral powder; the concentration of the sodium hydroxide solution is 6 mol / L, and the amount added is 35% of the mass of the surface-treated mineral powder; the amount of diethylenetriamine added is 22% of the mass of the surface-treated mineral powder.

[0167] The stirring rate is 550 r / min; the centrifugal rate is 3500 r / min; the washing adopts an ethanol solution with a mass fraction of 90%; the drying temperature is 55° C. and the drying time is 5 hours.

[0168] S5, load

[0169] The plant extract was added to deionized water and stirred for 15 minutes to obtain a plant extract solution, and then the modified mineral powder was added to the plant extract solution and stirred at 35° C. for 40 minutes, and then dried to obtain the modified extract mineral powder.

[0170] The plant extracts include pteris viridis extract, purslane extract, aloe vera extract and wormwood extract in a mass ratio of 1:1:1:1, and have a particle size of 150 nm.

[0171] The mass ratio of the plant extract to deionized water is 1:5.

[0172] The added amount of the modified mineral powder is 16% of the mass of the plant extract.

[0173] The stirring rate is 250 r / min, the drying temperature is 55° C., and the drying time is 5 h.

[0174] S6, Hybrid

[0175] The modified extract mineral powder and soluble protein were added into deionized water and stirred for 15 minutes to obtain a protein complex solution.

[0176] The mass ratio of the modified extract mineral powder, soluble protein micropowder and deionized water is 25:15:105.

[0177] The soluble protein is milk protein, and the particle size is 2 μm.

[0178] The stirring rate is 450 r / min.

[0179] S7, cross-linking

[0180] The nascent fiber is immersed in the protein composite liquid, heated to 140°C for reaction for 20 minutes, and then washed, dried and oiled to obtain the protein composite fiber.

[0181] The drying temperature is 85° C. and the drying time is 3 hours; the oiling agent used in the oiling is TK-1259.

[0182] The protein composite fiber prepared in Example 4 has a breaking strength of 4.83 cN / dtex, a fiber regain of 3.8%, a protein content of 12.3%, an antibacterial rate against Staphylococcus aureus of 98.6%, an antibacterial rate against Escherichia coli of 97.4%, and an antibacterial rate against Candida albicans of 96.8% after washing 50 times. The DPPH free radical scavenging rate is 78%, the ammonia removal rate is 98.5%, the acetic acid removal rate is 95.1%, and the isovaleric acid removal rate is 94.3%. After washing 50 times, the average loss rate of plant extracts and proteins is 0.85%.

[0183] Comparative Example 1

[0184] Representative Example 1 was selected as Comparative Example 1, with the S2 pretreatment step removed and the rest being consistent with Example 1.

[0185] The protein composite fiber prepared in Comparative Example 1 has a dry strength of 2.6 cN / dtex, a wet strength of 1.82 cN / dtex, a fiber regain of 14.1%, a protein content of 8.8%, an antibacterial rate against Staphylococcus aureus of 93.5%, an antibacterial rate against Escherichia coli of 92.3%, and an antibacterial rate against Candida albicans of 92.5%. The DPPH free radical scavenging rate is 73%, the ammonia removal rate is 91.7%, the acetic acid removal rate is 90.8%, and the isovaleric acid removal rate is 90.1%. After washing 50 times, the average loss rate of plant extracts and proteins is 2.52%.

[0186] Comparative Example 2

[0187] Representative Example 4 was selected as Comparative Example 2, with the S2 pretreatment step removed and the rest being consistent with Example 1.

[0188] The protein composite fiber prepared in Comparative Example 2 has a breaking strength of 3.94 cN / dtex, a fiber regain of 1.8%, a protein content of 8.2%, an antibacterial rate against Staphylococcus aureus of 92.2%, an antibacterial rate against Escherichia coli of 91.7%, and an antibacterial rate against Candida albicans of 92% after washing 50 times. The DPPH free radical scavenging rate is 71%, the ammonia removal rate is 91.1%, the acetic acid removal rate is 90.3%, and the isovaleric acid removal rate is 90%. After washing 50 times, the average loss rate of plant extracts and proteins is 2.97%.

[0189] Comparative Example 3

[0190] Representative Example 1 was selected, the modified mineral powder was removed, and unmodified bentonite was directly used as the mineral powder. The temperature in S7 was set to 50°C, and the rest was consistent with Example 1. As Comparative Example 3, the loading rate of the unmodified mineral powder on the plant extract was 67%.

[0191] The protein composite fiber prepared in Comparative Example 3 has a dry strength of 2.02 cN / dtex, a wet strength of 0.98 cN / dtex, a fiber regain of 13.9%, a protein content of 7.5%, an antibacterial rate against Staphylococcus aureus of 81.7%, an antibacterial rate against Escherichia coli of 80.6%, and an antibacterial rate against Candida albicans of 81.4% after washing 50 times, a DPPH free radical scavenging rate of 60%, an ammonia removal rate of 85.5%, an acetic acid removal rate of 83.2%, and an isovaleric acid removal rate of 82.8%. After washing 50 times, the average loss rate of plant extracts and proteins is 46%.

[0192] Comparative Example 4

[0193] Representative Example 4 was selected, the modified mineral powder was removed, and unmodified bentonite was directly used as the mineral powder. The temperature in S7 was set to 50°C, and the rest was consistent with Example 4. As Comparative Example 4, the loading rate of the unmodified mineral powder on the plant extract was 67%.

[0194] The protein composite fiber prepared by Comparative Example 4 has a breaking strength of 3.14 cN / dtex, a fiber regain of 1.7%, a protein content of 6.9%, an antibacterial rate against Staphylococcus aureus of 80.6%, an antibacterial rate against Escherichia coli of 79.4%, and an antibacterial rate against Candida albicans of 78.8% after washing 50 times, a DPPH free radical scavenging rate of 58%, an ammonia removal rate of 83.7%, an acetic acid removal rate of 82.9%, and an isovaleric acid removal rate of 82.4%. After washing 50 times, the average loss rate of plant extracts and proteins is 49%.

[0195] Comparative Examples 1 and 2, without pretreatment, had denser internal fiber structures, causing subsequent crosslinking reactions to primarily occur on the fiber surface, resulting in relatively reduced fiber strength and functional durability. Comparative Examples 3 and 4, because the mineral powder was not modified, no crosslinking reaction occurred between the fiber and protein. Instead, the three interacted physically, resulting in significant water loss. Furthermore, the unmodified mineral powder easily agglomerated and became unevenly distributed within the fiber, causing small bumps on the fiber surface and a decrease in fiber strength.

[0196] Unless otherwise specified, the ratios and percentages described in the present invention are all by mass; all raw materials are commercially available.

[0197] Finally, it should be noted that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art will be able to modify the technical solutions described in the aforementioned embodiments or substitute equivalents for some of the technical features. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A method for preparing a protein composite fiber, characterized in that: The preparation method includes spinning, pretreatment, surface treatment, preparation of modified mineral powder, loading, mixing and cross-linking; The cross-linking is as follows: immersing the nascent fiber in a protein composite liquid, heating it to 130-150° C. and reacting it for 10-30 minutes, and then washing it with water, drying it, and applying oil to obtain the protein composite fiber.

2. The method for preparing a protein composite fiber according to claim 1, characterized in that: The pretreatment is to hydrolyze the spun fibers to obtain pretreated spun fibers.

3. The method for preparing a protein composite fiber according to claim 1, characterized in that: The surface treatment comprises the following steps: adding the mineral powder to deionized water and ultrasonically dispersing the mixture for 2 to 5 minutes; adding an epoxy silane coupling agent and stirring the mixture for 10 to 15 minutes; adjusting the pH to 8 to 10 and heating the mixture to 60 to 70° C. for reaction for 30 to 40 minutes; grafting epoxy groups on the surface of the mineral powder; and after the reaction is completed, centrifuging, filtering, washing, and naturally drying the mineral powder to obtain the surface-treated mineral powder.

4. The method for preparing a protein composite fiber according to claim 3, characterized in that: The mineral powder is one or more of zeolite, medical stone, quartz stone, montmorillonite, sepiolite, and bentonite, and has a particle size of 1 to 2 μm; The epoxysilane coupling agent is one or more of 3-(2,3-epoxypropyloxy)propylmethyldimethoxysilane, 3-(2,3-epoxypropyloxy)propylmethyldiethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and the added amount is 25-35% of the mass of the mineral powder.

5. The method for preparing a protein composite fiber according to claim 1, characterized in that: The modified mineral powder is prepared by adding the surface-treated mineral powder to deionized water and stirring for 15 to 30 minutes, adding a catalyst and continuing to stir for 1 to 2 minutes, then adding 1,2-propylene glycol and sodium hydroxide solution, heating to 50 to 60° C. and stirring to react for 2 to 3 hours, then adding diethylenetriamine and continuing to stir to react for 90 to 120 minutes, cooling to room temperature after the reaction is completed, centrifuging, filtering, washing, and drying to obtain the modified mineral powder.

6. The method for preparing a protein composite fiber according to claim 5, characterized in that: The catalyst is one or more of BF3 and SnCl4, and the amount added is 1-1.5% of the mass of the surface-treated mineral powder; The amount of 1,2-propylene glycol added is 13-17% of the mass of the surface-treated mineral powder; the concentration of the sodium hydroxide solution is 4-8 mol / L, and the amount added is 30-40% of the mass of the surface-treated mineral powder; the amount of diethylenetriamine added is 18-24% of the mass of the surface-treated mineral powder.

7. The method for preparing a protein composite fiber according to claim 1, characterized in that: The loading method comprises adding the plant extract into deionized water and stirring for 10 to 20 minutes to obtain a plant extract solution, then adding the modified mineral powder into the plant extract solution and stirring at 30 to 40° C. for 30 to 50 minutes, and drying to obtain the modified extract mineral powder.

8. The method for preparing a protein composite fiber according to claim 7, characterized in that: The plant extract is one or more of pteris viridis extract, purslane extract, aloe vera extract, wormwood extract, ginger extract, mint extract, camellia extract, marigold extract, isatis leaf extract, and sarcandra extract, and the particle size is 100-200 nm; The added amount of the modified mineral powder is 15-18% of the mass of the plant extract.

9. The method for preparing a protein composite fiber according to claim 1, characterized in that: The mixing step is to add the modified extract mineral powder and soluble protein into deionized water and stir for 10 to 20 minutes to obtain a protein complex solution; The mass ratio of the modified extract mineral powder, the soluble protein micropowder and the deionized water is 20-30:13-18:100-110.

10. The method for preparing a protein composite fiber according to claim 9, characterized in that: The soluble protein is one or more of cashmere protein, oat protein, milk protein, collagen, soy protein, silk fibroin, feather protein, quinoa protein, silkworm pupa protein, pearl protein, keratin, silk protein, corn protein, peanut protein, casein, goat milk protein, polygonatum protein, poria protein, aloe protein, phycocyanin, whey protein, peptide protein, pea protein, and wheat germ protein, and the particle size is 2 to 4 μm.