Preparation method of antibacterial, mildew-proof and deodorant collagen cellulose fiber

Abstract

The invention belongs to the technical field of cellulose fibers, and particularly relates to a preparation method of antibacterial, mildew-proof and deodorant collagen cellulose fibers, which comprises the steps of preparation of a composite collagen assistant, preparation of a cellulose spinning stock solution, spinning and post-treatment. The preparation method comprises the following steps: firstly, carrying out selective oxidation on microcrystalline cellulose to obtain dialdehyde cellulose, and carrying out Schiff base reaction on amino on collagen and aldehyde on dialdehyde cellulose molecules to generate imine bonds; the rare earth ions interact with imine groups in the grafted protein, so that the prepared antibacterial, mildew-proof and deodorizing collagen cellulose fiber has high machining performance, also has the characteristics of antibacterial property, deodorization, mildew resistance, high wet modulus and the like, and is natural, degradable, safe and environment-friendly. Moreover, the collagen content in the collagen fiber prepared by the invention is as high as 30-40wt%, which is far beyond the protein content in the conventional collagen fiber.

Description

Technical Field

[0001] This invention belongs to the field of cellulose fiber technology, specifically, it is a method for preparing antibacterial, antifungal, and deodorizing collagen cellulose fibers. Background Technology

[0002] Collagen is a biological macromolecule, mainly found in the skin, bones, tendons, ligaments, and blood vessels of animals. Based on its distribution and functional characteristics in the body, collagen can be divided into interstitial collagen, basement membrane collagen, and peripheral collagen. Collagen molecules have a triple helix structure composed of three α-peptide chains twisted together, with the three chains interlocked by hydrogen bonds, making its molecular structure very stable. Interstitial collagen accounts for the vast majority of collagen in the body, mainly distributed in tissues such as skin and tendons. It includes type I, II, and III collagen. Type I collagen is rich in alanine and glycosylated hydroxylysine, accounting for about 80% to 90% of the total collagen in the human body. Its molecular structure is a tightly packed coarse fiber with a relatively large diameter of about 50-100 nm. It has extremely strong tensile strength, can promote blood circulation, repair damaged cells, and promote the growth of new cells. It has good biocompatibility, biodegradability, and bioactivity. Type III collagen is a fine fibrous collagen with a diameter of only 20-30 nm. Its molecular arrangement is loose and network-like, with better elasticity, more like an "elastic net", which can bring good elasticity and cushioning capacity to tissues.

[0003] Collagen and cellulose are both linear macromolecules with certain structural similarities, making them easy to combine and biocompatible. Given the excellent wearability of cellulose fibers, the combination of the two will undoubtedly be a manifestation of the functionalization and biomimicry of cellulose fibers, and has good research and development value.

[0004] However, when collagen is exposed to high temperatures and acidic or alkaline environments, the triple helix structure of collagen molecules usually changes, the molecular chains become loose, and the mechanical strength and thermal stability are also affected. As a result, the prepared collagen composite fibers can only retain a small portion of the original excellent properties of collagen. Therefore, traditional collagen fibers have low strength and low content of effective active protein components, ultimately making it difficult to meet the required antibacterial, antifungal, and deodorizing effects.

[0005] Patent application number 201310588899.9 discloses a method for preparing collagen fibers, the resulting product, and its applications. This method uses animal leather as raw material to directly extract natural collagen fibers. In today's society, animal leather cannot meet people's demand for collagen fibers, and its cost is far greater than that of synthetic fibers and cotton fibers. Patent application number 201611163216.5 discloses collagen cellulose fibers and its preparation method. This method grafts collagen onto cellulose using epichlorohydrin. The collagen cellulose fibers prepared have a low collagen content, only 5-15%. Patent application number 202011456297.4 discloses a method for preparing collagen regenerated cellulose fibers. The collagen fibers prepared by this method have a low collagen content and are only distributed on the fiber surface.

[0006] To address the aforementioned deficiencies, this invention provides a method for preparing antibacterial, antifungal, and deodorizing collagen cellulose fibers, thereby solving the problems of low collagen content and low fiber strength in existing collagen cellulose fibers, while simultaneously improving the antibacterial, antifungal, and deodorizing effects of the fibers. Summary of the Invention

[0007] To address the problems existing in the prior art, this invention proposes a method for preparing antibacterial, antifungal, and deodorizing collagen cellulose fibers, the preparation method comprising the following steps: S1. Preparation of compound collagen adjuvant S11, Preprocessing Microcrystalline cellulose was added to deionized water to prepare a suspension, and the suspension was ultrasonically treated for 3-8 minutes. The treated sample was repeatedly washed with deionized water and filtered, then centrifuged and vacuum dried.

[0008] Preferably, the mass fraction of microcrystalline cellulose in the suspension is 1-2%.

[0009] Preferably, the frequency of the ultrasonic treatment is 20–50 kHz.

[0010] Preferably, the centrifugation time is 15-20 min; the drying temperature is 90-105℃; and the drying time is 2-3 h.

[0011] S12, selective oxidation Pretreated microcrystalline cellulose was dissolved in sodium periodate solution and stirred at 40–50 °C for 90–120 min at a stirring rate of 500–600 r / min under light-protected conditions. After the reaction was completed, the mixture was filtered, and the filter cake was washed 2–3 times with deionized water. The filter cake was then placed in a 0.1–0.15 mol / L ethylene glycol solution and reacted for 20–30 min to remove unreacted sodium periodate. The mixture was then washed thoroughly with deionized water 2–3 times to remove ethylene glycol. The mixture was then vacuum dried at 45–80 °C for 5–7 h to obtain dialdehyde cellulose.

[0012] Preferably, the molar ratio of the microcrystalline cellulose to sodium periodate in the sodium periodate solution is 1:2 to 3.

[0013] Preferably, the concentration of the sodium periodate solution is 0.03–0.04 mol / L, and the pH is 2–2.5.

[0014] S13, Collagen Modification Water-soluble collagen was added to deionized water and stirred to dissolve, obtaining a collagen solution. Dialdehyde cellulose was added to deionized water and ultrasonically dispersed to obtain a dialdehyde cellulose dispersion. The collagen solution was added to the dialdehyde cellulose dispersion, and the pH was adjusted to 5-6 with dilute hydrochloric acid solution. The mixture was stirred at 40-45℃ for 60-80 min, and a Schiff base reaction occurred between the collagen and dialdehyde cellulose, successfully grafting collagen onto dialdehyde cellulose. After the reaction, the mixture was concentrated under reduced pressure at 40-45℃, filtered, and washed 2-3 times with deionized water. The grafted protein was then vacuum dried at 40-45℃ for 5-7 h.

[0015] Preferably, the ultrasonic dispersion frequency is 20–40 kHz and the duration is 3–7 min.

[0016] Preferably, the mass ratio of dialdehyde cellulose to deionized water is 1:10-12; and the mass ratio of water-soluble collagen to deionized water is 1:6-8.

[0017] Preferably, the mass fraction of the dilute hydrochloric acid solution is 1-2%.

[0018] Preferably, the mass ratio of dialdehyde cellulose to collagen is 1:2 to 4.

[0019] S14, rare earth coordination Lanthanum oxide was added to a 3-5 mol / L hydrochloric acid solution at a mass ratio of 1:1.5-2, and ultrasonically treated at 30-40℃ for 50-70 min at an ultrasonic frequency of 100-160 kHz. After the reaction was complete, the solution was evaporated and concentrated at 50-60℃, cooled to 0-5℃ for crystallization, and dried at 100-120℃ for 2-3 h to obtain lanthanum chloride. Lanthanum chloride was dissolved in anhydrous ethanol, and then grafted protein was added and stirred for 20-30 minutes. The pH was adjusted to 6-7 with sodium hydroxide solution, and the mixture was heated to 35-45℃ for 4-6 hours. After cooling to room temperature, 70±5wt% of anhydrous ethanol was removed by vacuum distillation. The precipitate was collected by centrifugation, washed, and dried to obtain the composite collagen adjuvant.

[0020] Preferably, the mass ratio of lanthanum chloride to anhydrous ethanol is 1:8 to 10.

[0021] Preferably, the mass ratio of lanthanum chloride to grafted protein is 1:4 to 9.

[0022] Preferably, the concentration of the sodium hydroxide solution is 0.2–0.5 mol / L.

[0023] S2. Preparation of cellulose spinning solution Alkali cellulose is produced by using wood pulp or bamboo pulp with a degree of polymerization of 700-900 as raw material, through impregnation, pressing, and pulverization; the alkali cellulose is then directly xanthated and dissolved without aging to obtain spinning slurry. The compound collagen functional additive was added to the spinning solution diluted 10 times with softened water and stirred evenly to obtain a compound collagen functional diluent with the effective collagen content adjusted to below 65%. The compound collagen functional diluent was added to the spinning solution, stirred evenly, filtered, and continuously degassed to obtain the cellulose spinning solution.

[0024] Preferably, during the impregnation process, an activator with a content of 0.05 to 0.1 wt% of methyl cellulose is added. The activator is one or a combination of several of polyethylene glycol alkylamines, polyethylene glycol alkyl ethers, polyethylene derivatives of aromatic compounds, and polyethylene glycol aliphatic derivatives.

[0025] Preferably, a denaturant with a content of 3.0 to 4.5 wt% methyl cellulose is added during dissolution. The denaturant is one or a combination of several of the following: polyoxyethylene, polyoxyethylene alkylamine, polyoxyolefin glycol, polyethylene glycol, polyethylene glycol alkylamine, aromatic alcohol, polyol, diethylamine, dimethylamine, and cyclohexylamine.

[0026] Preferably, the spinning solution contains 8.8–9.2 wt% methyl ester, 5.8–6.2 wt% alkali, 85–100 s falling ball viscosity, ≥60 esterification degree, ≥10 mL curing degree, and 23–25 °C.

[0027] Preferably, the amount of the compound collagen functional diluent added is such that the collagen content in the compound collagen functional diluent accounts for 30-40 wt% of the methylcellulose content.

[0028] S4, spinning Cellulose spinning solution is ejected from the spinneret and drawn into the coagulation bath to obtain nascent fiber bundles. The nascent fiber bundles are drawn through the spinning disc and then enter the plasticizing bath. After plasticizing and drawing, they are washed with water, bundled, cut, and enter the refining post-treatment stage.

[0029] Preferably, the nozzle draw is -10 to 10%, the spinning disc draw is 30 to 45%, the plasticizing draw is 8 to 10%, and the total draw is 120 to 130%.

[0030] Preferably, the concentrations of each component in the coagulation bath are: sulfuric acid 80-90 g / L, zinc sulfate 50-60 g / L, sodium sulfate 150-170 g / L, temperature 38-42℃, spinning rate 35-40 m / min, and immersion length 1000-1200 mm.

[0031] Preferably, the temperature in the plasticizing bath is 95-98°C, and the concentration of sulfuric acid is 20-25 g / L.

[0032] S5, Post-processing After being cut, the fibers are desulfurized with sodium sulfite, washed with water, and oiled to obtain collagen cellulose fibers.

[0033] Due to the adoption of the above technical solution, the beneficial effects of the present invention are as follows: 1. The collagen cellulose fiber prepared by this invention has excellent mechanical properties, as well as antibacterial, deodorizing, mildew-proof, and high wet modulus characteristics. It is also naturally biodegradable, safe and environmentally friendly.

[0034] 2. The collagen cellulose fibers prepared by this invention have a dry strength of 2.83–3.0 cN / dtex, a wet strength of 1.76–1.98 cN / dtex, and a wet modulus of 0.44–0.47 cN / dtex.

[0035] 3. The collagen fiber prepared by this invention has a collagen content as high as 30-40 wt%, which is about twice that of conventional collagen cellulose fiber. The two-stage mixing method ensures mild fiber forming conditions, preserving the collagen structure and resulting in better fiber mechanical properties. The fiber achieves a mildew resistance level of 0 (as determined by GB / T 24346-2009), exhibits inhibition rates greater than 99% against Escherichia coli, Staphylococcus aureus, and Candida albicans (as determined by GB / T 20944.3-2008), and an inhibition rate greater than 90% against Trichophyton rubrum (as determined by AATCC100-2019), demonstrating a significant effect in preventing athlete's foot. The fiber also has deodorizing effects, achieving an ammonia removal rate of 86% and an acetic acid removal rate of 82.8% (as determined by GB / T 33610.3-2019).

[0036] 4. This invention first obtains dialdehyde cellulose by selective oxidation of microcrystalline cellulose. Then, it utilizes the Schiff base reaction between the amino groups on collagen and the aldehyde groups on the dialdehyde cellulose molecules to generate imine bonds. Next, rare earth ions interact with the imine groups in the grafted protein, and the carbonyl oxygen on the imine groups coordinates with the rare earth elements to form stronger hydrogen bonds, improving the stability of the imine bonds under acidic conditions. Simultaneously, it makes the collagen molecular structure more compact and stable. The enhanced structural and thermal stability makes the collagen less prone to denaturation under high temperature and acid / alkali conditions. Furthermore, the addition of rare earth elements further enhances the antibacterial effect of the additives. The two have a synergistic effect, resulting in antibacterial, antifungal, and deodorizing collagen cellulose fibers with high mechanical processing properties and enhanced functionality.

[0037] 5. The addition of rare earth elements can improve the antibacterial and antifungal effects of fibers. However, conventional addition can also cause the loss of rare earth elements due to the influence of acids and alkalis. By using the imine bonds in grafted proteins to coordinate rare earth ions, not only can the structural stability and thermal stability of collagen be enhanced, but the loss rate of rare earth ions during fiber preparation is also reduced. According to spectral analysis, the loss rate of rare earth elements in cellulose fibers prepared by this method is less than 0.1%. Detailed Implementation

[0038] To further illustrate the technical means and effects of the present invention in achieving the intended purpose, the following detailed description of the specific implementation methods, structures, features and effects of the present invention, in conjunction with preferred embodiments, is provided below.

[0039] Example 1: A method for preparing antibacterial, antifungal, and deodorizing collagen cellulose fiber, the preparation method comprising the following steps; S1. Preparation of compound collagen adjuvant S11, Preprocessing Microcrystalline cellulose was added to deionized water to prepare a suspension, and the suspension was sonicated for 5 minutes. The treated sample was repeatedly washed with deionized water and filtered, then centrifuged and vacuum dried.

[0040] The mass fraction of microcrystalline cellulose in the suspension is 1.5%.

[0041] The frequency of the ultrasonic treatment is 30 kHz.

[0042] The centrifugation time was 20 minutes; the drying temperature was 95°C and the drying time was 2.5 hours.

[0043] S12, selective oxidation Pretreated microcrystalline cellulose was dissolved in sodium periodate solution and stirred at 45°C for 100 min at a stirring rate of 550 r / min under light-protected conditions. After the reaction was completed, the mixture was filtered, and the filter cake was washed three times with deionized water. The filter cake was then placed in 0.12 mol / L ethylene glycol solution and reacted for 25 min to remove unreacted sodium periodate. The mixture was then washed three times with deionized water to remove ethylene glycol. The mixture was then vacuum dried at 65°C for 6 h to obtain dialdehyde cellulose.

[0044] The molar ratio of the microcrystalline cellulose and sodium periodate in the sodium periodate solution is 1:2.5.

[0045] The sodium periodate solution has a concentration of 0.04 mol / L and a pH of 2.

[0046] S13, Collagen Modification Water-soluble collagen was added to deionized water and stirred to dissolve, obtaining a collagen solution. Dialdehyde cellulose was added to deionized water and ultrasonically dispersed to obtain a dialdehyde cellulose dispersion. The collagen solution was added to the dialdehyde cellulose dispersion, and the pH was adjusted to 5.5 with dilute hydrochloric acid solution. The mixture was stirred at 40°C for 70 min, and a Schiff base reaction occurred between the collagen and dialdehyde cellulose, successfully grafting collagen onto dialdehyde cellulose. After the reaction, the mixture was concentrated under reduced pressure at 40°C, filtered, washed three times with deionized water, and vacuum dried at 43°C for 6 h to obtain the grafted protein.

[0047] The ultrasonic dispersion frequency was 30 kHz, and the duration was 5 min.

[0048] The mass ratio of dialdehyde cellulose to deionized water is 1:11; the mass ratio of water-soluble collagen to deionized water is 1:7.

[0049] The mass fraction of the dilute hydrochloric acid solution is 1.5%.

[0050] The mass ratio of dialdehyde cellulose to collagen is 1:3.

[0051] S14, rare earth coordination Lanthanum oxide was added to a 4 mol / L hydrochloric acid solution at a mass ratio of 1:1.7, and ultrasonically treated at 35°C for 60 min at an ultrasonic frequency of 120 kHz. After the reaction was complete, the solution was evaporated and concentrated at 55°C, cooled to 5°C to crystallize, and dried at 110°C for 2.5 h to obtain lanthanum chloride. Lanthanum chloride was dissolved in anhydrous ethanol, and then grafted protein was added and stirred for 25 min. The pH was adjusted to 6.5 with sodium hydroxide solution, and the mixture was heated to 40 °C for 5 h. After cooling to room temperature, 70 wt% of anhydrous ethanol was removed by vacuum distillation. The precipitate was collected by centrifugation, washed, and dried under vacuum at 50 °C for 6 h to obtain a composite collagen adjuvant.

[0052] The mass ratio of lanthanum chloride to anhydrous ethanol is 1:9.

[0053] The mass ratio of lanthanum chloride to grafted protein is 1:6.

[0054] The concentration of the sodium hydroxide solution is 0.4 mol / L.

[0055] S2. Preparation of cellulose spinning solution Using wood pulp with a degree of polymerization of 800 as raw material, alkali cellulose is produced through impregnation, pressing, and pulverization; the alkali cellulose is directly xanthated and dissolved without aging to obtain spinning slurry; The compound collagen functional additive was added to the spinning solution diluted 10 times with softened water and stirred evenly to obtain a compound collagen functional diluent with an effective collagen content adjusted to 62%. The compound collagen functional diluent was added to the spinning solution, stirred evenly, filtered, and continuously degassed to obtain the cellulose spinning solution.

[0056] During the impregnation process, an activator with a content of 0.08 wt% methyl cellulose is added, and the activator is polyethylene glycol alkyl ether.

[0057] A denaturant containing 3.6 wt% methyl methacrylate, wherein the denaturant is a polyoxyethylene alkylamine, is added during dissolution.

[0058] The spinning solution contains 9 wt% methyl ester, 6 wt% alkali, has a falling ball viscosity of 90 s, a degree of esterification of 65, a degree of maturity of 13 mL, and a solution temperature of 24℃.

[0059] The amount of the compound collagen functional diluent added is such that the collagen content in the compound collagen functional diluent accounts for 34 wt% of the methylcellulose content.

[0060] S3, spinning Cellulose spinning solution is ejected from the spinneret and drawn into the coagulation bath to obtain nascent fiber bundles. The nascent fiber bundles are drawn through the spinning disc and then enter the plasticizing bath. After plasticizing and drawing, they are washed with water, bundled, cut, and enter the refining post-treatment stage.

[0061] The nozzle has a draw ratio of 5%, the spinning disc has a draw ratio of 35%, the plasticizing draw ratio is 9%, and the total draw ratio is 125%. The concentrations of each component in the coagulation bath are: sulfuric acid 80 g / L, zinc sulfate 60 g / L, sodium sulfate 150 g / L, temperature 40℃, spinning rate 35 m / min, and immersion length 1100 mm.

[0062] The temperature in the plasticizing bath was 96°C, and the concentration of sulfuric acid was 22 g / L.

[0063] S4, Post-processing After being cut, the fibers are desulfurized with sodium sulfite, washed with water, and oiled to obtain collagen cellulose fibers.

[0064] Example 2: A method for preparing antibacterial, antifungal, and deodorizing collagen cellulose fiber, the preparation method comprising the following steps; S1. Preparation of compound collagen adjuvant S11, Preprocessing Microcrystalline cellulose was added to deionized water to prepare a suspension, and the suspension was sonicated for 3 minutes. The treated sample was repeatedly washed with deionized water, filtered, centrifuged, and then vacuum dried.

[0065] The mass fraction of microcrystalline cellulose in the suspension is 1%.

[0066] The frequency of the ultrasonic treatment is 50 kHz.

[0067] The centrifugation time was 15 minutes; the drying temperature was 90°C and the drying time was 3 hours.

[0068] S12, selective oxidation Pretreated microcrystalline cellulose was dissolved in sodium periodate solution and stirred at 40°C for 90 min at a stirring rate of 500 r / min under light-protected conditions. After the reaction was completed, the mixture was filtered, and the filter cake was washed twice with deionized water. The filter cake was then placed in 0.1 mol / L ethylene glycol solution and reacted for 20 min to remove unreacted sodium periodate. It was then washed twice with deionized water to remove ethylene glycol. The mixture was then vacuum dried at 45°C for 5 h to obtain dialdehyde cellulose.

[0069] The molar ratio of the microcrystalline cellulose and sodium periodate in the sodium periodate solution is 1:2.

[0070] The sodium periodate solution has a concentration of 0.03 mol / L and a pH of 2.5.

[0071] S13, Collagen Modification Water-soluble collagen was added to deionized water and stirred to dissolve, obtaining a collagen solution. Dialdehyde cellulose was added to deionized water and ultrasonically dispersed to obtain a dialdehyde cellulose dispersion. The collagen solution was added to the dialdehyde cellulose dispersion, and the pH was adjusted to 5 with dilute hydrochloric acid solution. The mixture was stirred at 40°C for 60 min, and a Schiff base reaction occurred between the collagen and dialdehyde cellulose, successfully grafting collagen onto dialdehyde cellulose. After the reaction, the mixture was concentrated under reduced pressure at 45°C, filtered, washed twice with deionized water, and vacuum dried at 40°C for 7 h to obtain the grafted protein.

[0072] The ultrasonic dispersion frequency was 20 kHz, and the duration was 7 min.

[0073] The mass ratio of dialdehyde cellulose to deionized water is 1:10; the mass ratio of water-soluble collagen to deionized water is 1:6.

[0074] The mass fraction of the dilute hydrochloric acid solution is 1%.

[0075] The mass ratio of dialdehyde cellulose to collagen is 1:2.

[0076] S14, rare earth coordination Lanthanum oxide was added to a 3 mol / L hydrochloric acid solution at a mass ratio of 1:1.5, and ultrasonically treated at 30°C for 50 min at an ultrasonic frequency of 100 kHz. After the reaction was complete, the solution was evaporated and concentrated at 50°C, cooled to 0°C to crystallize, and dried at 100°C for 2 h to obtain lanthanum chloride. Lanthanum chloride was dissolved in anhydrous ethanol, and then grafted protein was added and stirred for 20 min. The pH was adjusted to 6 with sodium hydroxide solution, and the mixture was heated to 35 °C for 4 h. After cooling to room temperature, 65 wt% of anhydrous ethanol was removed by vacuum distillation. The precipitate was collected by centrifugation, washed, and dried under vacuum at 50 °C for 6 h to obtain a composite collagen adjuvant.

[0077] The mass ratio of lanthanum chloride to anhydrous ethanol is 1:8.

[0078] The mass ratio of lanthanum chloride to grafted protein is 1:4.

[0079] The concentration of the sodium hydroxide solution is 0.2 mol / L.

[0080] S2. Preparation of cellulose spinning solution Using wood pulp with a degree of polymerization of 700 as raw material, alkali cellulose is produced through impregnation, pressing, and pulverization; the alkali cellulose is directly xanthated and dissolved without aging to obtain spinning slurry; The compound collagen functional additive was added to the spinning solution diluted 10 times with softened water and stirred evenly to obtain a compound collagen functional diluent with an effective collagen content adjusted to 62%. The compound collagen functional diluent was added to the spinning solution, stirred evenly, filtered, and continuously degassed to obtain the cellulose spinning solution.

[0081] During the impregnation process, an activator with a content of 0.05 wt% methyl cellulose is added, and the activator is polyethylene glycol alkylamine.

[0082] A denaturant containing 3.0 wt% methyl methacrylate, wherein the denaturant is a polyoxyethylene alkylamine, is added during dissolution.

[0083] The spinning solution contains 8.8 wt% methyl ester, 5.8 wt% alkali, has a falling ball viscosity of 85 s, a degree of esterification of 62, a degree of maturity of 12 mL, and a solution temperature of 23℃.

[0084] The amount of the compound collagen functional diluent added is such that the collagen content in the compound collagen functional diluent accounts for 32 wt% of the methylcellulose content.

[0085] S3, spinning Cellulose spinning solution is ejected from the spinneret and drawn into the coagulation bath to obtain nascent fiber bundles. The nascent fiber bundles are drawn through the spinning disc and then enter the plasticizing bath. After plasticizing and drawing, they are washed with water, bundled, cut, and enter the refining post-treatment stage.

[0086] The nozzle has a draw ratio of -10%, the spinning disc has a draw ratio of 45%, the plasticizing draw ratio is 8%, and the total draw ratio is 120%.

[0087] The concentrations of each component in the coagulation bath are: sulfuric acid 90 g / L, zinc sulfate 50 g / L, sodium sulfate 170 g / L, temperature 38℃, spinning rate 40 m / min, and immersion length 1000 mm.

[0088] The temperature in the plasticizing bath is 98°C, and the concentration of sulfuric acid is 20 g / L.

[0089] S4, Post-processing After being cut, the fibers are desulfurized with sodium sulfite, washed with water, and oiled to obtain collagen cellulose fibers.

[0090] Example 3: A method for preparing antibacterial, antifungal, and deodorizing collagen cellulose fiber, the preparation method comprising the following steps; S1. Preparation of compound collagen adjuvant S11, Preprocessing Microcrystalline cellulose was added to deionized water to prepare a suspension, and the suspension was sonicated for 8 minutes. The treated sample was repeatedly washed with deionized water and filtered, then centrifuged and vacuum dried.

[0091] The mass fraction of microcrystalline cellulose in the suspension is 2%.

[0092] The frequency of the ultrasonic treatment is 20 kHz.

[0093] The centrifugation time was 20 minutes; the drying temperature was 105°C and the drying time was 2 hours.

[0094] S12, selective oxidation Pretreated microcrystalline cellulose was dissolved in sodium periodate solution and stirred at 50°C for 120 min at a stirring rate of 600 r / min under light-protected conditions. After the reaction was completed, the mixture was filtered, and the filter cake was washed three times with deionized water. The filter cake was then placed in 0.15 mol / L ethylene glycol solution and reacted for 30 min to remove unreacted sodium periodate. The mixture was then washed three times with deionized water to remove ethylene glycol. The mixture was then vacuum dried at 80°C for 7 h to obtain dialdehyde cellulose.

[0095] The molar ratio of the microcrystalline cellulose and sodium periodate solution is 1:3.

[0096] The sodium periodate solution has a concentration of 0.04 mol / L and a pH of 2.

[0097] S13, Collagen Modification Water-soluble collagen was added to deionized water and stirred to dissolve, obtaining a collagen solution. Dialdehyde cellulose was added to deionized water and ultrasonically dispersed to obtain a dialdehyde cellulose dispersion. The collagen solution was added to the dialdehyde cellulose dispersion, and the pH was adjusted to 6 with dilute hydrochloric acid solution. The mixture was stirred at 45°C for 80 min, and a Schiff base reaction occurred between the collagen and dialdehyde cellulose, successfully grafting collagen onto dialdehyde cellulose. After the reaction, the mixture was concentrated under reduced pressure at 45°C, filtered, washed twice with deionized water, and vacuum dried at 45°C for 5 h to obtain the grafted protein.

[0098] The ultrasonic dispersion frequency is 20–40 kHz, and the duration is 3–7 min.

[0099] The mass ratio of dialdehyde cellulose to deionized water is 1:12; the mass ratio of water-soluble collagen to deionized water is 1:8.

[0100] The mass fraction of the dilute hydrochloric acid solution is 2%.

[0101] The mass ratio of dialdehyde cellulose to collagen is 1:4.

[0102] S14, rare earth coordination Lanthanum oxide was added to a 5 mol / L hydrochloric acid solution at a mass ratio of 1:2, and ultrasonically treated at 40°C for 70 min at an ultrasonic frequency of 160 kHz. After the reaction was complete, the solution was evaporated and concentrated at 60°C, cooled to 5°C to crystallize, and dried at 120°C for 3 h to obtain lanthanum chloride. Lanthanum chloride was dissolved in anhydrous ethanol, and then grafted protein was added and stirred for 30 min. The pH was adjusted to 7 with sodium hydroxide solution, and the mixture was heated to 45 °C for 6 h. After cooling to room temperature, 75 wt% of anhydrous ethanol was removed by vacuum distillation. The precipitate was collected by centrifugation, washed, and dried under vacuum at 50 °C for 6 h to obtain the composite collagen adjuvant.

[0103] The mass ratio of lanthanum chloride to anhydrous ethanol is 1:10.

[0104] The mass ratio of lanthanum chloride to grafted protein is 1:9.

[0105] The concentration of the sodium hydroxide solution is 0.5 mol / L.

[0106] S2. Preparation of cellulose spinning solution Bamboo pulp with a degree of polymerization of 900 is used as raw material and alkali cellulose is produced by impregnation, pressing and crushing; the alkali cellulose is directly xanthated and dissolved without aging to obtain spinning slurry; The compound collagen functional additive was added to the spinning solution diluted 10 times with softened water and stirred evenly to obtain a compound collagen functional dilution with an effective collagen content adjusted to 64%. The compound collagen functional dilution was added to the spinning solution, stirred evenly, filtered, and continuously degassed to obtain cellulose spinning solution.

[0107] During the impregnation process, an activator with a content of 0.1 wt% of methyl cellulose is added, and the activator is polyethylene glycol alkylamine.

[0108] A denaturant containing 4.5 wt% methyl methacrylate, wherein the denaturant is a polyoxyethylene alkylamine, is added during dissolution.

[0109] The spinning solution contains 9.2 wt% methyl ester, 6.2 wt% alkali, has a falling ball viscosity of 100 s, a degree of esterification of 66, a degree of maturity of 14 mL, and a solution temperature of 25 °C.

[0110] The amount of the compound collagen functional diluent added is such that the collagen content in the compound collagen functional diluent accounts for 36 wt% of the methylcellulose content.

[0111] S3, spinning Cellulose spinning solution is ejected from the spinneret and drawn into the coagulation bath to obtain nascent fiber bundles. The nascent fiber bundles are drawn through the spinning disc and then enter the plasticizing bath. After plasticizing and drawing, they are washed with water, bundled, cut, and enter the refining post-treatment stage.

[0112] The nozzle has a draw ratio of 10%, the spinning disc has a draw ratio of 30%, the plasticizing draw ratio is 10%, and the total draw ratio is 130%.

[0113] The concentrations of each component in the coagulation bath are: sulfuric acid 85 g / L, zinc sulfate 55 g / L, sodium sulfate 160 g / L, temperature 42℃, spinning rate 37 m / min, and immersion length 1200 mm.

[0114] The temperature in the plasticizing bath is 95°C, and the concentration of sulfuric acid is 25 g / L.

[0115] S4, Post-processing After being cut, the fibers are desulfurized with sodium sulfite, washed with water, and oiled to obtain collagen cellulose fibers.

[0116] Comparative Example 1: A representative example 1 was selected, with step S14 removed, and all other steps were the same as in Example 1, and this was used as Comparative Example 1.

[0117] Comparative Example 2: A representative example, Example 1, was selected. Step S1 was removed, and in step S2, the compound collagen functional agent was directly replaced with an equal amount of collagen. All other steps were the same as in Example 1. This was used as Comparative Example 2.

[0118] Comparative Example 3: A representative example, Example 1, was selected. In step S2, the composite collagen functional diluent was not used. Instead, the composite collagen functional aid was directly added to the spinning solution and mixed evenly. All other steps were the same as in Example 1. This example serves as Comparative Example 3.

[0119] Examples 1-3 were tested for antibacterial, antifungal, and deodorizing properties. The specific results are shown in Table 1.

[0120] Table 1 Testing items Example 1 Example 2 Example 3 Anti-mildew rating 0 0 0 Escherichia coli inhibition rate (%) ＞99% ＞99% ＞99% Staphylococcus aureus (%) ＞99% ＞99% ＞99% Candida albicans (%) ＞99% ＞99% ＞99% Red hairy fungus (%) 92 91 94 Ammonia removal rate (%) 85.1 84.4 86 Acetic acid removal rate (%) 82.2 81.3 82.8 Mechanical properties and protein content of Examples 1-3 and Comparative Examples 1-3 were tested, and the specific results are shown in Tables 2 and 3.

[0121] Table 2 Testing items Example 1 Example 2 Example 3 Dry strength (cN / dtex) 3.0 2.83 2.92 Wet strength (cN / dtex) 1.98 1.76 1.84 Wet modulus (cN / dtex) 0.47 0.44 0.45 Protein content in fiber (wt%) 33.9 31.6 35.7 Table 3 Testing items Comparative Example 1 Comparative Example 2 Comparative Example 3 Dry strength (cN / dtex) 2.47 2.25 2.68 Wet strength (cN / dtex) 1.31 1.1 1.56 Wet modulus (cN / dtex) 0.28 0.2 0.32 Protein content in fiber (wt%) 29.3 14.5 31.2 As can be seen from Table 1, the collagen cellulose fiber prepared by the present invention has excellent antibacterial, antifungal and deodorizing effects, and its functionality is more complete.

[0122] As can be seen from Tables 2 and 3, the collagen cellulose fibers prepared using Examples 1-3 not only have excellent mechanical properties, but also have a high collagen content.

[0123] Comparative Example 1 removed the rare earth coordination step, resulting in a decrease in the mechanical properties and protein content of the fiber. This is because the coordination of rare earth can make the molecular structure and imine bonds of collagen more stable, making the structure of the active protein components less susceptible to damage while maintaining the strength of the fiber.

[0124] In Comparative Example 2, the composite collagen functional additive was directly replaced with an equal amount of collagen. The mechanical properties and protein content of the fiber decreased significantly. This is because the collagen denatures under the influence of acid and alkali environments during the preparation of cellulose fibers, which not only greatly affects the strength of the fiber, but also causes a large amount of collagen to be lost.

[0125] Comparative Example 3 did not use the two-stage mixing method, resulting in some additives sticking to the stirring rod or wall, causing waste; the fiber strength decreased slightly because the two-stage mixing method resulted in more uniform and better compatibility of the compound collagen functional additives in the cellulose spinning solution.

[0126] Unless otherwise specified, all proportions and percentages mentioned in this invention are mass proportions and mass percentages; all raw materials are commercially available.

[0127] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A method for preparing antibacterial, antifungal, and deodorizing collagen cellulose fibers, characterized in that, The preparation method comprises preparation of a composite collagen auxiliary agent, preparation of a cellulose spinning dope, spinning and post-treatment; The preparation of the composite collagen auxiliary agent comprises the following steps: S11, pretreatment: Microcrystalline cellulose is added to deionized water to prepare a suspension, and the treated sample is repeatedly washed and filtered under centrifugation, and then vacuum dried after centrifugation; S12, selective oxidation: The pretreated microcrystalline cellulose is dissolved in a sodium periodate solution, and stirred at 40-50℃ for 90-120min at a stirring rate of 500-600r / min, and the reaction is carried out in the dark; after the reaction is completed, filtration is performed, the filter cake is washed with deionized water for 2-3 times, then the filter cake is placed in a 0.1-0.15mol / L ethylene glycol solution for 20-30min, and then washed with deionized water for 2-3 times, and vacuum dried at 45-80℃ for 5-7h to obtain dialdehyde cellulose; S13, collagen modification: The water-soluble collagen is added to deionized water and stirred to dissolve, to obtain a collagen solution; the dialdehyde cellulose is added to deionized water and ultrasonically dispersed to obtain a dialdehyde cellulose dispersion; the collagen solution is added to the dialdehyde cellulose dispersion, and a dilute hydrochloric acid solution is used to adjust the pH to 5-6, and then stirred at 40-45℃ for 60-80min; after the reaction is completed, vacuum concentration is performed at 40-45℃, filtration is performed, and the filter cake is washed with deionized water for 2-3 times, and then vacuum dried at 40-45℃ for 5-7h to obtain grafted protein; S14, rare earth coordination: Lanthanum oxide is added to a 3-5mol / L hydrochloric acid solution at a mass ratio of 1:1.5-2, and ultrasonically treated at 30-40℃ for 50-70min at an ultrasonic frequency of 100-160kHz; after the reaction is completed, evaporation concentration is performed at 50-60℃, and then cooled to 0-5℃ for crystallization, and dehydrated by drying at 100-120℃ for 2-3h to obtain lanthanum chloride; The lanthanum chloride is dissolved in anhydrous ethanol, and then the grafted protein is added and stirred for 20-30min; a sodium hydroxide solution is used to adjust the pH to 6-7, and then heated to 35-45℃ for 4-6h; after cooling to room temperature, 70±5wt% of the anhydrous ethanol is removed by vacuum distillation, and the precipitate is collected by centrifugation, washed and dried to obtain the composite collagen auxiliary agent.

2. The method of claim 1, wherein the anti-bacterial, anti-mildew, and deodorant collagen cellulose fiber is prepared by adding 0.1 to 5 parts by weight of the anti-bacterial, anti-mildew, and deodorant agent to 100 parts by weight of the collagen cellulose fiber. In S11, the mass fraction of microcrystalline cellulose in the suspension is 1-2%, the ultrasonic treatment frequency is 20-50kHz, the centrifugation time is 15-20min, and the drying temperature is 90-105℃, and the drying time is 2-3h.

3. The method of claim 1, wherein the anti-bacterial, anti-mildew and deodorant collagen cellulose fiber is prepared by adding 0.1 to 5 wt% of the anti-bacterial, anti-mildew and deodorant collagen cellulose fiber to a collagen fiber solution, and then drying the collagen fiber solution. In S12, the molar ratio of microcrystalline cellulose to sodium periodate in the sodium periodate solution is 1:2-3; In S12, the concentration of the sodium periodate solution is 0.03-0.04mol / L, and the pH is 2-2.

5.

4. The method of claim 1, wherein the anti-bacterial, anti-mildew and deodorant collagen cellulose fiber is prepared by adding 0.1 to 5 wt% of the anti-bacterial, anti-mildew and deodorant agent to the collagen fiber and then drying the same. In S13, the mass ratio of dialdehyde cellulose to deionized water is 1:10-12, the mass ratio of water-soluble collagen to deionized water is 1:6-8, and the mass ratio of dialdehyde cellulose to collagen is 1:2-4.

5. The method of claim 1, wherein the anti-bacterial, anti-mildew and deodorant collagen cellulose fiber is prepared by adding 0.1 to 5 wt% of the anti-bacterial, anti-mildew and deodorant agent to the collagen fiber and then drying the same. In S14, the mass ratio of lanthanum chloride to anhydrous ethanol is 1:8-10, and the mass ratio of lanthanum chloride to grafted protein is 1:4-9. The concentration of the sodium hydroxide solution in the S14 is 0.2-0.5 mol / L.

6. The method of claim 1, wherein the anti-bacterial, anti-mildew, and deodorant collagen cellulose fiber is prepared by adding 0.1 to 5 wt% of the anti-bacterial, anti-mildew, and deodorant agent to the collagen fiber, and then drying the collagen fiber. The preparation of the cellulose spinning dope is as follows: wood pulp or bamboo pulp with a polymerization degree of 700-900 is used as raw material, and the alkali cellulose is prepared by dipping, pressing and crushing; the alkali cellulose is directly yellowed and dissolved to prepare the spinning glue solution; The composite collagen functional additive is added into the spinning glue solution diluted 10 times with softened water to stir uniformly, so as to obtain the composite collagen functional diluent with the effective content of collagen being adjusted to 65% or less; the composite collagen functional diluent is added into the spinning glue solution to stir uniformly, filter and continuously defoam, so as to obtain the cellulose spinning dope.

7. The method of claim 6, wherein the anti-bacterial, anti-mildew, and deodorant collagen cellulose fiber is prepared by adding 0.1 to 5 parts by weight of the anti-bacterial, anti-mildew, and deodorant agent to 100 parts by weight of the collagen fiber, and then drying the mixture. The activator with a methylene content of 0.05-0.1 wt% is added during the dipping, and the activator is one or a combination of polyethylene glycol alkyl amine, polyethylene glycol alkyl ether, polyethylene derivative of aromatic compound, polyethylene glycol aliphatic derivative; The denaturant with a methylene content of 3.0-4.5 wt% is added during the dissolving, and the denaturant is one or a combination of polyoxyethylene, polyoxyethylene alkyl amine, polyalkylene oxide glycol, polyethylene glycol, polyethylene glycol alkyl amine, aromatic alcohol, polyol, diethylamine, dimethylamine and cyclohexylamine.

8. The method of claim 6, wherein the anti-bacterial, anti-mildew, and deodorant collagen cellulose fiber is prepared by adding 0.1 to 5 parts by weight of the anti-bacterial, anti-mildew, and deodorant agent to 100 parts by weight of the collagen fiber. The spinning glue solution contains 8.8-9.2 wt% of methylene, 5.8-6.2 wt% of alkali, the falling ball viscosity is 85-100 s, the esterification degree is greater than or equal to 60, the aging degree is greater than or equal to 10 mL, and the glue solution temperature is 23-25℃; The adding amount of the composite collagen functional diluent is 30-40 wt% of the methylene content in the composite collagen functional diluent.

9. The method of claim 1, wherein the anti-bacterial, anti-mildew, and deodorant collagen cellulose fiber is prepared by adding 0.1 to 5 parts by weight of the anti-bacterial, anti-mildew, and deodorant agent to 100 parts by weight of the collagen fiber, and then drying the mixture. The spinning is as follows: the cellulose spinning dope is sprayed from the spinneret, stretched by the spinneret, enters the coagulation bath to obtain the primary fiber tows, the primary fiber tows are stretched by the spinning disc, enter the plasticizing bath, are washed after plasticizing stretching, are cut after bundling, and enter the refining post-processing stage; The spinneret stretching is-10-10%, the spinning disc stretching is 30-45%, the plasticizing stretching is 8-10%, and the total stretching is 120-130%; The concentration of each component in the coagulation bath is as follows: sulfuric acid 80-90 g / L, zinc sulfate 50-60 g / L, sodium sulfate 150-170 g / L, the temperature is 38-42℃, the spinning speed is 35-40 m / min, and the dipping length is 1000-1200 mm; In the plasticizing bath, the temperature is 95-98℃, and the concentration of sulfuric acid is 20-25 g / L.

10. The method for preparing antibacterial, antifungal, and deodorizing collagen cellulose fiber according to claim 1, characterized in that, The post-processing is as follows: the cut fibers are desulfurized by sodium sulfite, washed and oiled to obtain the collagen cellulose fibers.