Healthcare functional protein composite fiber spinning solution and production method thereof

Abstract

The invention relates to spinning of composite fibers. The protein composite fiber spinning solution with the health-care function comprises a zinc chloride aqueous solution containing protein molecules and polyacrylonitrile macromolecules, the protein comprises animal protein, plant protein and a flame retardant, and 1-4 micromolecular drugs with bacteriostatic and bactericidal performance are grafted on the protein molecules. The small molecule medicine comprises the following components: extracts in sappan wood, including hematoxylin, homoisoflavone and hematoxychalcone, and an extract of golden cypress, including berberine, also called berberine; the flame retardant is a water-soluble halogen-free environment-friendly flame retardant and comprises a phosphorus-nitrogen compound. According to the production method of the spinning solution, after protein is dissociated, the micromolecule medicine is added, so that the micromolecule medicine with the bacteriostatic and bactericidal performance is grafted to protein macromolecules, the fiber has the bacteriostatic and bactericidal performance, and therefore the effect that clothes have the long-acting bacteriostatic and bactericidal health-care effect is truly achieved, and the cost is low.

Description

Technical Field

[0001] The present invention relates to the spinning of composite fibers, and particularly to a spinning dope for protein composite fibers. Background Art

[0002] Existing artificially synthesized animal and plant protein fibers mainly include milk protein fibers, soybean protein fibers, and animal and plant protein synthetic fibers (animal proteins include casein, cortical collagen protein, and hair keratin; plant proteins include by-products cake and residue of various oil crops). In the production of the above protein fibers, the spinning dope is the key to fiber production.

[0003] Currently, for various fibers obtained by copolymerizing existing animal, plant, and animal-plant double proteins with polyvinyl alcohol or polyacrylonitrile, although they have good moisture absorption, moisture release, air permeability, skin-friendly property, and comfort; however, the hair dissolution process uses mercaptoacetic acid and mercaptoethanol with relatively high toxicity as dissociating agents. The market price of both dissociating agents is more than 20,000 yuan per ton, the cost is relatively high, and the pollution is serious. If spinning and weaving are carried out into fabrics and then made into related products in contact with the human body without proper subsequent cleaning, there are potential safety hazards to the human body.

[0004] On the other hand, there are some so-called antibacterial fabrics on the market. Most of them mix metal wires with certain antibacterial effects such as silver wires during the spinning process in order to achieve antibacterial effects. Not to mention the high price of such metals, the properties of the metals themselves will affect the feel of the fabrics. Summary of the Invention

[0005] The present invention aims to solve the above-mentioned defects of the prior art and provides a spinning dope for health-care functional protein composite fibers and its production method. The present invention can reduce the raw material cost, improve the touch of the product, and has a certain antibacterial effect.

[0006] The spinning dope for protein composite fibers with health-care functions of the present invention includes an aqueous zinc chloride solution containing protein molecules and polyacrylonitrile macromolecules, 1 to 4 kinds of small molecule drugs with antibacterial and bactericidal properties grafted on the protein molecules, protein including animal protein and plant protein, a flame retardant, the animal protein including cortical collagen protein, hair keratin, wool produced by the coarse-haired goat breed, and the waste wool combed down by wool textile enterprises; the plant protein including by-products cake and residue of oil crops after oil extraction; the small molecule drugs including: extracts from sappanwood including hematoxylin, homoisoflavone, sappanchalcone, and extracts from phellodendron amurense including berberine; the flame retardant is selected from water-soluble halogen-free environmentally friendly flame retardants, including phosphorus-nitrogen composites.

[0007] The protein composite fiber spinning dope with health care function, wherein the flame retardant is a water-soluble flame retardant comprising a composition of flame retardant ZJ150 and Doher-6502-1.

[0008] The protein composite fiber spinning dope with health care function, wherein the spinning dope comprises the following substances in parts by weight: 0-40 parts of vegetable protein and 40-0 parts of animal protein; 1-5 parts of small molecule drug; 43-80 parts of polyacrylonitrile: 0-20 parts of flame retardant.

[0009] A production method of the protein composite fiber spinning dope with health care function, which comprises:

[0010] Hair dissolution step: Add 55-65% zinc chloride aqueous solution into the reaction kettle, the addition amount is 13-18 times of the net weight of the hair, then add 1.8-3% pure hydrogen peroxide based on the net weight of the hair, add the purified hair while heating, stirring and raising the temperature to 65-75 °C, keep the temperature and stir slowly for dissolution for 180-240 min, then raise the temperature to 95-98 °C, stir and dissolve for 30-50 min, after observing full dissolution under a microscope, cool down to 50-60 °C and filter to obtain a protein solution for use.

[0011] Polyacrylonitrile dissolution step: Select a wool-like polymer for polyacrylonitrile, with a molecular weight of 80,000 Daltons, and fully dissolve it with zinc chloride aqueous solution for use.

[0012] Mixing reaction step: According to the formula amount, slowly add the prepared protein solution into the reaction kettle of the dissolved polyacrylonitrile while stirring, stir and keep at 55-65 °C, then add 1-5 parts of the small molecule drug, 0-20 parts of water-soluble flame retardant ZJ150 and 20-0 parts of Doher-6502-1, and stir and react for 60-120 min.

[0013] After filtration and defoaming, the spinning dope can be obtained and sent to the spinning process.

[0014] The molecules of these small molecule drugs selected in the present invention respectively contain a carbonyl group, an aldehyde group or a ketone group; the carbonyl group is prone to undergo an addition reaction with hydrogen in water to become a carbonyl aldehyde, while aldehydes and ketones can be oxidized to carboxyl groups in an acidic or alkaline environment. The carboxyl group and the amino group on the amino acid in the protein undergo a dehydration reaction to form an amide bond - a peptide bond. Therefore, the small molecule drugs are linked to the protein molecule through their amide bonds. Thus, the present invention grafts small molecule drugs with antibacterial and bactericidal properties onto protein molecules and polyacrylonitrile macromolecules, making the fiber itself have antibacterial and bactericidal properties, so as to truly achieve the long-term antibacterial and bactericidal health care effect of the clothing itself. The traditional hair dissolution process uses expensive mercaptoacetic acid and highly toxic mercaptoethanol as dissociating agents, and the prices of both products are more than 20,000 yuan per ton, and the pollution is serious. The present invention uses inexpensive hydrogen peroxide that has no pollution after the reaction; it not only solves the pollution but also greatly reduces the cost and production safety. Its advantages are very obvious. The animal protein described in the present invention comes from the wool of rough-haired breed goats or the fallen wool combed from cotton in wool textile enterprises; the plant protein is the protein extracted from the by-product cake of various oil crops; the raw materials are all waste materials, turning waste into treasure and greatly reducing the cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] The present invention will be further described below with reference to the accompanying drawings:

[0016] Figure 1 is the flow block diagram of the present invention. SPECIFIC EMBODIMENTS

[0017] Please refer to Figure 1 , the protein of the present invention includes animal protein / or plant protein, the animal protein is the wool of rough-haired breed goats or the fallen wool combed from cotton in wool textile enterprises; the plant protein is the protein extracted from the by-product cake of various oil crops; the small molecule drugs include: hematoxylin, high isoflavone, hematoxylinchalcone; berberine, also known as berberine; the flame retardant mainly selects water-soluble halogen-free environmentally friendly flame retardants (phosphorus-nitrogen composites).

[0018] The present invention will be further described below in combination with the production steps:

[0019] 1. Hair dissolution: Add a 55-65% zinc chloride aqueous solution to the reaction kettle, the addition amount is 13-18 times the net weight of the hair, and then add 1.8-3% of pure hydrogen peroxide based on the net weight of the hair. While heating up, stirring and adding the purified hair, heat up to 65-75 °C, keep the temperature and slowly stir and dissolve for 180-240 min, then heat up to 95-98 °C, stir and dissolve for 30-50 min. After observing full dissolution under a microscope, cool down to 50-60 °C. Then, it is filtered roughly and finely for later use.

[0020] 2. Dissolution of commercial casein: Add an aqueous zinc chloride solution with a weight concentration of 55-65% to the dissolution kettle. The addition amount is 7-13 times the weight of the casein. When the temperature is raised to 35-45°C, add commercial casein while stirring, keep warm and stir for soaking for 30-60 min, then raise the temperature to 90-98°C while stirring, and keep warm and stir for 60-90 min. Observe with a microscope for complete dissolution, and use it after filtration.

[0021] 3. Separation of protein: Add an aqueous zinc chloride solution with a weight concentration of 55-65% to the dissolution kettle. The addition amount is 7-13 times the weight of the separated protein. When the temperature is raised to 35-45°C, add hydrogen peroxide-separated protein while stirring, keep warm and stir for soaking for 20-40 min, then raise the temperature to 90-98°C while stirring, and keep warm and stir for 60-90 min. Observe with a microscope for complete dissolution, and use it after filtration.

[0022] 4. Take any 1-5 parts of commercial hematoxylin or high isoflavone or hematoxychalcone or berberine, or the sum of any 2 or any 3 or 4 of them, 1-5 parts, and set aside for use.

[0023] 5. Water-soluble flame retardant: Take flame retardant ZJ150 or flame retardant Doher-6502-1 or 50% of each of them. The effective ingredient of the taken amount accounts for 5-15% of the total amount of protein and polyvinyl cyanide, and dissolve it in a 60% aqueous zinc chloride solution for use.

[0024] 6. Dissolution of polyvinyl cyanide:

[0025] (1). Swelling of polyvinyl cyanide: Select a wool-like polymer for polyvinyl cyanide, and its molecular weight is preferably 80,000 daltons. Add an aqueous zinc chloride solution with a concentration of 30-45% to the reaction kettle. The addition amount is 3-5 times the amount of polyvinyl cyanide. Raise the temperature to 40-50°C, add polyvinyl cyanide powder while stirring, and keep the temperature at 30-35°C after addition. Keep warm and soak for 60-120 min to allow the powder to swell fully for easy dissolution.

[0026] (2). Dissolution of polyvinyl cyanide: While stirring and heating, add zinc chloride powder to the reaction kettle that has been fully swollen, so that the weight concentration of the aqueous zinc chloride solution reaches 55-65% and the temperature reaches 55-60°C. Keep warm and stir for 120-240 min. Observe with a microscope for complete dissolution and set aside for use.

[0027] Take any one of the protein solutions of 1., 2., or 3. that have been dissolved and are ready for use, or take 50% of each of any two of them, 4. a small molecule drug, and 5. a flame retardant, and slowly add them one by one while stirring to 6. a polyacrylonitrile solution. At this time, adjust the weight concentration of the solvent zinc chloride to 60% with an aqueous zinc chloride solution, and make the sum of the weights of the four substances of protein, polyacrylonitrile, small molecule drug, and flame retardant account for 8-13% of the total liquid weight concentration. Keep the temperature at 55-60°C and stir for 60-90 minutes. Filter and let it stand for defoaming for 6-8 hours. This is the spinning dope to be used. Feed it into the spinning machine. By replacing spinnerets with different pore sizes, functional protein composite clothing fibers or fibers for wigs with bactericidal and antibacterial health care functions can be spun.

[0028] The following further illustrates the present invention in conjunction with embodiments:

[0029] Taking the preparation of 10000 Kg of dope at one time and spinning 1000 Kg of fibers as an example, the weight concentration of the total effective components of the spinable fibers accounts for 10% of the total liquid weight concentration; the weight concentration of the aqueous zinc chloride solution as the solvent is 60%. The weight concentrations of the components in the liquid are as follows: 280 Kg of protein, accounting for 28% of the effective components; 635 Kg of polyacrylonitrile, accounting for 63.5% of the effective components; 25 Kg of small molecule drug, accounting for 2.5% of the effective components; 60 Kg of flame retardant, accounting for 6% of the effective components; 9000 Kg of 60% aqueous zinc chloride solution, accounting for 90% of the total liquid weight, among which 5400 Kg is zinc chloride and 3600 Kg is water.

[0030] Example 1. Dissolution and preparation of each substance

[0031] Example 1.1 Hair dissolution: Add 847.4 Kg of softened water (excluding the natural water content in the hair) to the reaction kettle, add 1631.5 Kg of zinc chloride powder while stirring and heating up, and obtain 2478.9 Kg of 65.8% aqueous zinc chloride solution. Add 18 Kg of 30% hydrogen peroxide (which does not participate in the reaction and only plays a catalytic role in hair dissociation), add 311.1 Kg of clean hair (with a water content of 10%) (equivalent to 280 Kg of pure hair) while stirring and heating up, accounting for 10% of the total liquid weight, and obtain a total liquid weight of 2808 Kg. Stir and heat up to 65-75°C, keep the temperature and stir slowly for dissolution for 180-240 minutes, heat up to 95-98°C, keep the temperature and stir slowly for dissolution for 30-50 minutes, observe under a microscope for complete dissolution, and cool down to 50-60°C. Then filter through coarse and fine filters for use.

[0032] Example 1.2. Dissolution of commercial casein: Add 850.9 Kg of softened water (excluding the natural water content in commercial casein) to the reaction kettle. While stirring, heating up, add 1638 Kg of zinc chloride powder. Then, a 65.8% zinc chloride aqueous solution of 2488.9 Kg is obtained. While stirring, heating up, add 311.1 Kg of commercial casein (with a water content of 10%) (equivalent to 280 Kg of pure casein), which accounts for 10% of the total liquid weight. Thus, the total liquid weight is 2800 Kg. While stirring, heat up to 40 - 45 °C and soak for 40 - 60 min. Then, while stirring, heat up to 93 - 98 °C and keep warm with slow stirring for dissolution for 90 - 120 min. Observe with a microscope until it is fully dissolved, and then cool down to 50 - 60 °C. Then, it is filtered through coarse and fine filters for standby.

[0033] Example 1.3. Dissolution of commercial separated protein: Add 850.9 Kg of softened water (excluding the natural water content in commercial separated protein) to the reaction kettle. While stirring, heating up, add 1638 Kg of zinc chloride powder. Then, a 65.8% zinc chloride aqueous solution of 2488.9 Kg is obtained. While stirring, heating up, add 311.1 Kg of commercial separated protein (with a water content of 10%) (equivalent to 280 Kg of pure separated protein), which accounts for 10% of the total liquid weight. Thus, the total liquid weight is 2800 Kg. While stirring, heat up to 40 - 45 °C and soak for 30 - 45 min. Then, while stirring, heat up to 93 - 98 °C and keep warm with slow stirring for dissolution for 60 - 90 min. Observe with a microscope until it is fully dissolved, and then cool down to 50 - 60 °C. Then, it is filtered through coarse and fine filters for standby.

[0034] Example 1.4. Take any 1 - 5 parts of commercial hematoxylin, or high isoflavones, or hematoxylinchalcone, or berberine, or the sum of any 2 or any 3 or 4 of them, totaling 25 Kg for standby.

[0035] Example 1.5. Water - soluble flame retardant: Take flame retardant ZJ150, or flame retardant Doher - 6502 - 1, or 50% of each of them. The effective ingredient of the taken amount is 60 Kg, accounting for 6% of the fiber effective ingredient, and dissolve it in 300 Kg of 60% zinc chloride aqueous solution for standby.

[0036] Example 1.6. Dissolution of polyacrylonitrile:

[0037] (1). Swelling of polyacrylonitrile: Select a wool - like polyacrylonitrile polymer, and its molecular weight is preferably 80000 Daltons. Add 1524 Kg of softened water and 1016 Kg of zinc chloride powder to the reaction kettle to obtain a 40% zinc chloride aqueous solution of 2540 Kg. Heat up to 45 °C, and while stirring, add 635 Kg of polyacrylonitrile powder, which accounts for 20% of the total liquid weight. Thus, the total liquid weight is 3175 Kg. Keep the temperature at 35 °C after adding, stir and keep warm for soaking for 90 min to allow the powder to swell fully for easy dissolution.

[0038] (2) Dissolution of polyacrylonitrile: While stirring, heating, and adding 1310 Kg of zinc chloride powder to the fully swollen reaction kettle, an aqueous zinc chloride solution with a weight of 3850 Kg is obtained, with a weight concentration reaching 60.416%, a polyacrylonitrile weight concentration of 14.16%, a total liquid volume of 4485 Kg, a temperature reaching 55 - 60 °C, and maintaining the temperature and stirring for 120 - 240 min. Observation with a microscope shows that it is fully dissolved and ready for use.

[0039] Example 2. Preparation of Spinning Dope

[0040] Example 2.1. While stirring, sequentially add the pre-dissolved protein solution, small molecule drug, and flame retardant from Examples 1.1, 1.4, and 1.5 to the reaction kettle containing the polyacrylonitrile solution from Example 1.6. Thus, a total liquid volume of 7670 Kg is obtained, where the solvent is 6660 Kg of an aqueous zinc chloride solution with a content of 62.125% (including 2522.5 Kg of water and 4137.5 Kg of zinc chloride), and the fiber effective component content is 1000 Kg (including 280 Kg of protein, 25 Kg of small molecule drug, 60 Kg of flame retardant, and 635 Kg of polyacrylonitrile), with the weight concentration of the fiber effective component being 13%. Maintain the temperature at 55 - 60 °C, and while stirring, add 2330 Kg of an aqueous zinc chloride solution with a weight concentration of 53.93% (including 1073.5 Kg of softened water and 1256.5 Kg of zinc chloride). Thus, a spinning dope with an aqueous zinc chloride solution weight concentration of 60%, a fiber effective component weight concentration of 10%, and a total solution volume of 10000 Kg is obtained. Maintain the temperature at 55 - 60 °C and stir for 60 - 90 min. Then filter, degas, send it to the spinning pressure regulating tank through a transfer pump, and send it to the spinneret of the spinning machine through a metering pump.

[0041] Example 2.2. While stirring, sequentially add the pre-dissolved protein solution, small molecule drug, and flame retardant from Examples 1.2, 1.4, and 1.5 to the reaction kettle containing the polyacrylonitrile solution from Example 1.6. Thus, a total liquid volume of 7678 Kg is obtained, where the solvent is 6678 Kg of an aqueous zinc chloride solution with a content of 62.13% (including 2534 Kg of water and 4144 Kg of zinc chloride), and the fiber effective component content is 1000 Kg (including 635 Kg of polyacrylonitrile, 280 Kg of protein, 25 Kg of small molecule drug, and 60 Kg of flame retardant), with the weight concentration of the fiber effective component being 13%. While stirring, add 2330 Kg of an aqueous zinc chloride solution (including 1073.5 Kg of softened water and 1256.5 Kg of zinc chloride), maintain the temperature at 55 - 60 °C, and stir for 60 - 90 min. Thus, a spinning dope with an aqueous zinc chloride solution weight concentration of 60%, a fiber effective component weight concentration of 10%, and a total solution volume of 10000 Kg is obtained. Then filter, degas, send it to the spinning pressure regulating tank through a transfer pump, and send it to the spinneret of the spinning machine through a metering pump.

[0042] Example 2.3. The protein solution, small molecule drug, and flame retardant that have been dissolved and are ready for use in Examples 1.2, 1.4, and 1.5 are successively added to the reaction kettle containing the polyacrylonitrile solution prepared in Example 1.6 while stirring. Thus, a liquid with a total amount of 7670 Kg is obtained, including 6670 Kg of an aqueous zinc chloride solution with a solvent content of 62.13% (where the water content is 2526 Kg and the zinc chloride content is 4144 Kg), and 1000 Kg of the effective fiber components (including 635 Kg of polyacrylonitrile, 280 Kg of protein, 25 Kg of small molecule drug, and 60 Kg of flame retardant). The weight concentration of the effective fiber components is 13%. Then, 2330 Kg of an aqueous zinc chloride solution with a weight concentration of 53.93% (where the softened water content is 1073.5 Kg and the zinc chloride content is 1256.5 Kg) is added while stirring, and the mixture is kept at 55 - 60 °C and stirred for 60 - 90 min. Thus, a spinning dope with a total solution amount of 10000 Kg is obtained, where the weight concentration of the aqueous zinc chloride solution is 60% and the weight concentration of the effective fiber components is 10%. Then, it is filtered, degassed, sent to the spinning pressure regulating tank through a transfer pump, and fed into the spinneret of the spinning machine through a metering pump.

[0043] Example 2.4. Take 50% of the protein solutions that have been dissolved and are ready for use from any two of Examples 1.1, 1.2, and 1.3, and the small molecule drug and flame retardant in Examples 1.4 and 1.5, and successively add them to the reaction kettle containing the polyacrylonitrile solution prepared in Example 1.6 while stirring. Thus, a liquid with a total amount of 7670 Kg is obtained, including 6670 Kg of an aqueous zinc chloride solution with a solvent weight concentration of 62.13% (where the water content is 2526 Kg and the zinc chloride content is 4144 Kg), and 1000 Kg of the effective fiber components (including 635 Kg of polyacrylonitrile, 280 Kg of protein, 25 Kg of small molecule drug, and 60 Kg of flame retardant). The weight concentration of the effective fiber components is 13%. Then, 2330 Kg of an aqueous zinc chloride solution with a weight concentration of 53.93% (where the softened water content is 1073.5 Kg and the zinc chloride content is 1256.5 Kg) is added while stirring, and the mixture is kept at 55 - 60 °C and stirred for 60 - 90 min. Thus, a spinning dope with a total solution amount of 10000 Kg is obtained, where the weight concentration of the aqueous zinc chloride solution is 60% and the weight concentration of the effective fiber components is 10%. Then, it is filtered, degassed, sent to the spinning pressure regulating tank through a transfer pump, and fed into the spinneret of the spinning machine through a metering pump.

[0044] Example 3. Dissolution and preparation of each substance

[0045] Example 3.1 Hair Dissolution: Add 970 Kg of softened water (excluding the natural water content in the hair) to the reaction kettle. While stirring, heating, and adding 1851 Kg of zinc chloride powder, a 65.62% zinc chloride aqueous solution of 2821 Kg is obtained. Add 23.47 Kg of 30% hydrogen peroxide (which does not participate in the reaction but only plays a role in catalyzing hair dissociation). While stirring, heating, and adding 355.5 Kg of clean hair (with a water content of 10%) (equivalent to 320 Kg of pure hair), accounting for 10% of the total liquid weight, so the total liquid weight is 3200 Kg. While stirring, heat up to 65 - 75 °C, keep warm and stir slowly for dissolution for 180 - 240 min, then heat up to 95 - 98 °C, keep warm and stir slowly for dissolution for 30 - 50 min. Observe with a microscope for complete dissolution, and then cool down to 50 - 60 °C. Then, it is filtered roughly and finely for standby.

[0046] Example 3.2. Commercial Casein Dissolution: Add 978.5 Kg of softened water (excluding the natural water content in the commercial casein) to the reaction kettle. While stirring, heating, and adding 1866 Kg of zinc chloride powder, a 65.6% zinc chloride aqueous solution of 2844.5 Kg is obtained. While stirring, heating, and adding 355.5 Kg of commercial casein (with a water content of 10%) (equivalent to 320 Kg of pure casein), accounting for 10% of the total liquid weight, so the total liquid weight is 3200 Kg. While stirring, heat up to 40 - 45 °C, soak for 40 - 60 min, then heat up to 93 - 98 °C, keep warm and stir slowly for dissolution for 90 - 120 min. Observe with a microscope for complete dissolution, and then cool down to 50 - 60 °C. Then, it is filtered roughly and finely for standby.

[0047] Example 3.3. Commercial Separated Protein Dissolution: Add 978.5 Kg of softened water (excluding the natural water content in the commercial separated protein) to the reaction kettle. While stirring, heating, and adding 1866 Kg of zinc chloride powder, a 65.6% zinc chloride aqueous solution of 2844.4 Kg is obtained. While stirring, heating, and adding 355.5 Kg of commercial separated protein (with a water content of 10%) (equivalent to 320 Kg of pure separated protein), accounting for 10% of the total liquid weight, so the total liquid weight is 3200 Kg. While stirring, heat up to 40 - 45 °C, soak for 30 - 45 min, then heat up to 93 - 98 °C, keep warm and stir slowly for dissolution for 60 - 90 min. Observe with a microscope for complete dissolution, and then cool down to 50 - 60 °C. Then, it is filtered roughly and finely for standby.

[0048] Example 3.4. Take any 1 - 5 parts of commercial hematoxylin or high isoflavone or hematoxylinchalcone or berberine, or the sum of any 2 or any 3 or 4 of them, a total of 40 Kg for standby.

[0049] Example 3.5. Water-soluble flame retardant: Take flame retardant ZJ150 or flame retardant Doher-6502-1 or 50% of each of them. The active ingredient taken is 90 Kg, accounting for 9% of the active ingredient of the fiber, and dissolve it in 450 Kg of 60% zinc chloride aqueous solution for standby.

[0050] Example 3.6. Dissolution of polyacrylonitrile:

[0051] (1). Swelling of polyacrylonitrile: The polyacrylonitrile selected is a wool-like polymer, and its molecular weight is preferably 80,000 daltons. Add 1320 Kg of softened water and 880 Kg of zinc chloride powder to the reaction kettle to obtain 2200 Kg of 40% zinc chloride aqueous solution. Heat up to 45 °C, and while stirring, add 550 Kg of polyacrylonitrile powder, accounting for 20% of the total weight of the liquid, that is, the total weight of the liquid is 2750 Kg. Keep the temperature at 35 °C after adding, stir and keep warm for 90 min to allow the powder to swell fully for easy dissolution.

[0052] (2). Dissolution of polyacrylonitrile: To the reaction kettle that has been fully swollen, while stirring and heating, add 1049 Kg of zinc chloride powder to obtain 3215 Kg of zinc chloride aqueous solution with a weight concentration of 60%, a polyacrylonitrile weight concentration of 14.6%, a total liquid volume of 3765 Kg, and a temperature reaching 55 - 60 °C. Keep warm and stir for 120 - 240 min. Observe with a microscope until it is fully dissolved for standby.

[0053] Example 4. Preparation of spinning dope

[0054] Example 4.1. Sequentially add the protein solution, small molecule drug, and flame retardant that have been dissolved and are ready for use in Examples 3.1, 3.4, and 3.5 to the reaction kettle where the polyacrylonitrile solution in Example 3.6 is ready for use while stirring, that is, obtain a total liquid volume of 7545 Kg, including 6545 Kg of 61.88% zinc chloride aqueous solution as the solvent (where the water content is 2495 Kg and the zinc chloride content is 4050 Kg), and 1000 Kg of fiber active ingredient content (including 320 Kg of protein, 40 Kg of small molecule drug, 90 Kg of flame retardant, and 550 Kg of polyacrylonitrile). The weight concentration of the fiber active ingredient is 13.25%. Keep warm at 55 - 60 °C, and then while stirring, add 2455 Kg of 54.99% zinc chloride aqueous solution (including 1105 Kg of softened water and 1350 Kg of zinc chloride), that is, obtain a spinning dope with a zinc chloride aqueous solution weight concentration of 60% and a fiber active ingredient weight concentration of 10% and a total solution volume of 10000 Kg. Keep warm at 55 - 60 °C and stir for 60 - 90 min. Then filter, defoam, send it to the spinning pressure regulating tank through a transfer pump, and send it to the spinneret of the spinning machine through a metering pump.

[0055] Example 4.2. The protein solution, small molecule drug, and flame retardant that had been dissolved and were ready for use in Examples 3.2, 3.4, and 3.5 were successively added to the reaction kettle containing the polyacrylonitrile solution prepared in Example 3.6 while stirring. Thus, a spinning dope with a total liquid volume of 7545 Kg was obtained, which included 6545 Kg of an aqueous zinc chloride solution with a solvent content of 62.11% (where the water content was 2480 Kg and the zinc chloride content was 4065 Kg), and 1000 Kg of fiber active ingredients (including 550 Kg of polyacrylonitrile, 320 Kg of protein, 40 Kg of small molecule drug, and 90 Kg of flame retardant). The weight concentration of the fiber active ingredients was 13.25%. Then, 2455 Kg of an aqueous zinc chloride solution with a weight concentration of 54.38% (including 1120 Kg of softened water and 1335 Kg of zinc chloride) was added while stirring, and the mixture was kept at 55 - 60 °C and stirred for 60 - 90 min. Thus, a spinning dope with a weight concentration of 60% of the aqueous zinc chloride solution, a weight concentration of 10% of the fiber active ingredients, and a total solution volume of 10000 Kg was obtained. Then, it was filtered, degassed, sent to the spinning pressure regulating tank through a transfer pump, and fed into the spinneret of the spinning machine through a metering pump.

[0056] Example 4.3. The protein solution, small molecule drug, and flame retardant that had been dissolved and were ready for use in Examples 3.3, 3.4, and 3.5 were successively added to the reaction kettle containing the polyacrylonitrile solution prepared in Example 3.6 while stirring. Thus, a spinning dope with a total liquid volume of 7545 Kg was obtained, which included 6545 Kg of an aqueous zinc chloride solution with a solvent content of 62.11% (where the water content was 2480 Kg and the zinc chloride content was 4065 Kg), and 1000 Kg of fiber active ingredients (including 550 Kg of polyacrylonitrile, 320 Kg of protein, 40 Kg of small molecule drug, and 90 Kg of flame retardant). The weight concentration of the fiber active ingredients was 13.25%. Then, 2455 Kg of an aqueous zinc chloride solution with a weight concentration of 54.38% (including 1120 Kg of softened water and 1335 Kg of zinc chloride) was added while stirring, and the mixture was kept at 55 - 60 °C and stirred for 60 - 90 min. Thus, a spinning dope with a weight concentration of 60% of the aqueous zinc chloride solution, a weight concentration of 10% of the fiber active ingredients, and a total solution volume of 10000 Kg was obtained. Then, it was filtered, degassed, sent to the spinning pressure regulating tank through a transfer pump, and fed into the spinneret of the spinning machine through a metering pump.

[0057] Example 4.4. Take 50% of any two of the dissolved and ready-to-use protein solutions in Examples 3.1, 3.2, and 3.3, and successively add the small molecule drugs and flame retardants in 3.4 and 3.5 to the reaction kettle for the polyacrylonitrile solution in Example 3.6 while stirring. Thus, an aqueous zinc chloride solution with a total liquid volume of 7545 Kg, where the solvent is 62.11% (6545 Kg of aqueous zinc chloride solution, with 2480 Kg of water content and 4065 Kg of zinc chloride content), and the fiber active ingredient content is 1000 Kg (including 550 Kg of polyacrylonitrile, 320 Kg of protein, 40 Kg of small molecule drug, and 90 Kg of flame retardant) is obtained. The weight concentration of the fiber active ingredient is 13.25%. Then, while stirring, add 2455 Kg of an aqueous zinc chloride solution with a weight concentration of 54.38% (including 1120 Kg of softened water and 1335 Kg of zinc chloride), keep the temperature at 55 - 60 °C, and stir for 60 - 90 min. Thus, a spinning dope with an aqueous zinc chloride solution weight concentration of 60%, a fiber active ingredient weight concentration of 10%, and a total solution volume of 10000 Kg is obtained. Then, filter, degas, send it to the spinning pressure regulating tank through a transfer pump, and send it to the spinneret of the spinning machine through a metering pump.

[0058] Note: The aqueous zinc chloride solution is used as the solvent for dissolving protein and polyacrylonitrile, and all the zinc chloride in it is recovered and reused repeatedly.

[0059] Using the same methods in Examples 1, 2, 3, and 4, the concentrations or component ratios of each component in the liquid can be adjusted to obtain spinning dopes with different component concentrations and ratios.

[0060] The obtained fibers are tested according to the following standards:

[0061] Actual moisture regain: GB / T9995 - 1997 (laboratory temperature 20 °C, relative humidity 65%);

[0062] Short fiber linear density: Refer to GB / T 14335 - 2008;

[0063] Short fiber breaking strength / elongation: Refer to GB / T 14337 - 2008;

[0064] The test results according to the above standards are shown in the following table:

[0065] Table:

[0066]

[0067] It can be seen from this that the obtained regenerated protein fibers have physical properties comparable to those of ordinary chemical fibers.

Claims

1. A protein composite fiber spinning solution with health care function, comprising a zinc chloride aqueous solution containing protein molecules and polyacrylonitrile macromolecules, wherein the protein comprises animal protein and plant protein, and a flame retardant, wherein the animal protein comprises cortical collagen protein, hair keratin protein, wool produced by coarse-haired goat breeds, and wool from wool spinning enterprises; the plant protein comprises cake byproduct of oil-pressing of oil crops; characterized in that: The protein molecule is grafted with 1 to 4 small molecule drugs with antibacterial and bactericidal properties, and the small molecule drugs include: extracts from sappan wood including hematoxylin, homoisoflavones, sappan chalcone, and extracts from Phellodendron amurense including berberine also known as berberine; the flame retardant is a water-soluble halogen-free environmentally friendly flame retardant, including a phosphorus-nitrogen complex.

2. The protein composite fiber spinning solution with health care function according to claim 1, characterized in that: The flame retardant is a water-soluble flame retardant comprising a composition of flame retardant ZJ150 and Doher-6502-1.

3. The protein composite fiber spinning solution with health care function according to claim 1, characterized in that: The spinning solution comprises the following substances in parts by weight: 0-40 parts of plant protein and 40-0 parts of animal protein; 1-5 parts of small molecule drugs; 43-80 parts of polyacrylonitrile; and 0-20 parts of flame retardant.

4. A method for producing a spinning solution of protein composite fibers with health care functions as claimed in claim 1, 2 or 3, characterized in that: It includes: Hair dissolving step: adding 55-65% zinc chloride aqueous solution to a reaction kettle, the amount of which is 13-18 times the net weight of the hair, and then adding 1.8-3% pure hydrogen peroxide of the net weight of the hair, adding the purified hair while heating and stirring, heating to 65-75° C., maintaining the temperature and slowly stirring and dissolving for 180-240 minutes, then heating to 95-98° C., stirring and dissolving for 30-50 minutes, observing under a microscope that the solution is fully dissolved, cooling to 50-60° C., filtering to obtain a protein solution for standby use; Polyacrylonitrile dissolving step: select a wool-like polymer of polyacrylonitrile with a molecular weight of 80,000 Daltons, and fully dissolve it in a zinc chloride aqueous solution for use; Mixing step: according to the formula amount, slowly add the protein solution to be used into the polyacrylonitrile reactor in which the protein solution has been dissolved while stirring, stir and maintain 55-65° C., then add 1-5 parts of the small molecule drug, 0-20 parts of the water-soluble flame retardant ZJ150, and 20-0 parts of Doher-6502-1, stir and react for 60-120 minutes; filter and degas to obtain the spinning solution.

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