CN107142543B - Animal colloidal protein composite apocynum venetum cellulose fiber and preparation method thereof - Google Patents
Animal colloidal protein composite apocynum venetum cellulose fiber and preparation method thereof Download PDFInfo
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- CN107142543B CN107142543B CN201710544945.3A CN201710544945A CN107142543B CN 107142543 B CN107142543 B CN 107142543B CN 201710544945 A CN201710544945 A CN 201710544945A CN 107142543 B CN107142543 B CN 107142543B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
- D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
Abstract
The invention provides an animal colloidal protein composite apocynum venetum cellulose fiber, which meets the following requirements: the dry breaking strength is more than or equal to 3.5cN/dtex, the wet breaking strength is more than or equal to 2.8cN/dtex, the animal colloidal protein content is more than or equal to 3 percent, the dry breaking elongation is 11-13 percent, and the wet breaking elongation is 11-14 percent. The invention also provides a preparation method of the animal colloidal protein composite apocynum venetum cellulose fiber, which comprises the steps of preparing a protein dissolving solution; the preparation method of the protein dissolving solution comprises the following steps: adding CHAPS, glycerol and thiourea into deionized water, stirring and dissolving to obtain CHAPS solution, adding animal colloidal protein powder into the CHAPS solution, stirring, ultrasonically dissolving, and keeping the temperature to obtain protein dissolved solution. The cellulose fiber prepared by the invention has good glossiness, the protein in the fiber keeps the softness and better draping feeling of the fiber, so that the prepared cellulose fiber has high strength and low elongation, and the animal colloidal protein in the fiber is not easy to run off.
Description
Technical Field
The invention relates to an animal colloidal protein cellulose fiber and a preparation method thereof, in particular to an animal colloidal protein composite apocynum venetum cellulose fiber and a preparation method thereof.
Background
The apocynum venetum stem skin is a good fiber raw material, is an ideal new natural textile raw material, and is known as the king of wild fiber. The clothing made by fine processing and spinning of the apocynum venetum fiber has the characteristics of good air permeability, strong hygroscopicity, softness, bacteriostasis, warmness in winter and coolness in summer and the like.
The apocynum venetum fiber is thinner than ramie, the single fiber strength is five times or six times higher than that of cotton, and the apocynum venetum fiber can be blended with cotton, wool or silk to be woven into various blended cotton cloth, wool fabric and silk fabrics. Blended with wool, such as damask, serge, vaseline, etc.; the cotton blended yarn has serge, gabardine, ramie yarn, etc.; the blended yarn with spun silk is the spun silk, etc. Compared with common fabrics, the apocynum venetum cloth has the advantages of better wear resistance and corrosion resistance, larger moisture absorption and smaller shrinkage, and is a variety with development prospect in the hemp fabrics.
The patent number is 201510176587.6, the patent name is a preparation method of viscose fiber containing apocynum venetum extract, which discloses an apocynum venetum extract viscose fiber, the prepared fiber is carried out by adding the apocynum venetum extract, so the prepared viscose fiber only has partial apocynum venetum functionality, the inherent advantages of strength and elongation of cellulose fiber prepared from natural apocynum venetum fiber are lost, the prepared fiber has overlarge dry and wet elongation at break, and the deformation is easily generated in the wearing and using process, thereby the attractiveness is influenced; meanwhile, the prepared apocynum venetum viscose fiber has too low antibacterial rate to candida albicans and does not have the function of releasing infrared rays.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the animal colloidal protein composite apocynum venetum cellulose fiber, the cellulose fiber prepared by the invention has good glossiness, the prepared cellulose fiber has high fiber strength and low elongation, the animal colloidal protein in the fiber is not easy to lose, and the cellulose fiber prepared by the invention meets the following indexes: the dry breaking strength is more than or equal to 3.5cN/dtex, the wet breaking strength is more than or equal to 2.8cN/dtex, the animal colloidal protein content is more than or equal to 3%, the dry breaking elongation is 11-13%, the wet breaking elongation is 11-14%, the fineness deviation rate is less than or equal to 1.5%, the linear density deviation rate is less than or equal to +/-3%, the residual sulfur content is less than or equal to 7mg/100g, the defects are less than or equal to 3mg/100g, the length-doubled fiber is less than or equal to 0.5mg/100mg, the length deviation rate is less than or equal to +/-2%, and the whiteness.
The fabric prepared by adopting the animal colloidal protein composite apocynum venetum cellulose fiber prepared by the invention is prepared according to GB-T20944.3-2008 part 3 of evaluation of antibacterial property of textile: according to the stipulation of the oscillation method, the antibacterial performance of the cellulose fiber prepared by the invention is detected by the national ecological textile quality supervision and inspection center, the inhibition rate of staphylococcus aureus reaches 97.0-98.3%, the inhibition rate of escherichia coli reaches 99.1-99.6%, and the inhibition rate of candida albicans reaches 99.2-99.8%.
The close-fitting fabric made of the cellulose fibers has good anti-radiation and far infrared emission performances, and the far infrared emission rate of the animal colloidal protein composite apocynum venetum cellulose fibers is 95.6-99.1% by adopting FZ/T64010 standard detection; due to excellent infrared emissivity, the manufactured clothes have the characteristics of heat retention of 2.5-3 times that of all-cotton underwear below 8 ℃, air permeability of 3.5 times that of pure cotton fabrics above 21 ℃, and unique 'warm in winter and cool in summer'.
The close-fitting fabric prepared from the cellulose fiber has good mite removing performance, and the mite removing rate of the animal colloidal protein composite apocynum venetum cellulose fiber prepared by the invention is 98.5-99.6% through the detection of GBT 24253-;
because the dry breaking elongation and the wet breaking elongation of the cellulose fiber prepared by the invention are lower, yarns, fabrics and clothes made of the cellulose fiber are hardly deformed and shrunk after being washed and used, and have good deformation resistance, and meanwhile, the natural characteristics of apocynum venetum are kept in the fiber, and the fiber has the effects of resisting radiation, emitting far infrared rays, resisting bacteria and delaying aging; the animal colloidal protein contained in the fiber can supplement amino acid for human body, and the prepared fiber is smooth and glossy, so that the prepared cellulose fiber has the characteristics of softness and fineness; the fabric made of the fiber is suitable for being used as close-fitting fabrics of underpants, socks, home wear, bedding and the like, can also be blended with cotton, terylene and the like, and has good antibacterial and anti-mildew properties and good insect and mite expelling and preventing functions; the cellulose fiber prepared by the method has good ultraviolet resistance, and can be used for manufacturing a close-fitting ultraviolet-resistant lining and the like.
The preparation process of the invention adopts the apocynum venetum pulp as the raw material, and the apocynum venetum pulp has the following relevant indexes: 650 percent of polymerization degree 550-3。
The second invention aims to provide a preparation method of animal colloidal protein composite apocynum venetum cellulose fiber, which comprises the following steps:
firstly, preparing apocynum venetum viscose liquid
(1) Preparing slurry porridge: the apocynum venetum pulp is crushed into pulp porridge with a certain concentration by a crusher, so that the reaction surface area is increased, the production efficiency is improved, and necessary conditions are provided for subsequent processes; the concentration of the slurry porridge is 400-450 g/L.
(2) Activating cellulose: adding hydrogen peroxide into the prepared apocynum venetum slurry porridge, and reacting for 30-50min after the slurry porridge is heated;
the concentration of hydrogen peroxide in the apocynum pulp porridge is 20-30 g/L;
heating the slurry porridge to 50-60 ℃; the mechanism of the step is that hydrogen peroxide has slow and moderate oxidation performance, on one hand, hemicellulose, ash, tannin and colloid in part of the apocynum pulp fibers are removed, on the other hand, hydrogen peroxide slowly releases lower bubbles to attach to the surfaces of the hemp fibers, the capillary space between the fibers is increased, the fibers are fully filled with micro bubbles, and the impregnation uniformity and the reaction performance of the hemp pulp are improved.
During the activation process of the cellulose, an activating agent dz-01 is preferably added; the concentration of the activating agent in the slurry is 1-3 g/L; the activating agent dz-01 is produced by Zibobi biological enzyme GmbH; the activator can protect alpha-cellulose in the hemp pulp from being degraded by hydrogen peroxide, and the bleaching effect of the hydrogen peroxide is avoided as much as possible.
(3) Primary squeezing: the primary pressing temperature is 26-32 ℃, and the pressing multiple is 1.6-2.3 times; the water and the hydrogen peroxide in the hemp pulp after the cellulose activation step can be extruded, and the hydrogen peroxide content is low, so that the extruded liquid can be recycled; after the step of activating the cellulose, the hydrogen peroxide increases the space between the apocynum fibers, a vacuum state is formed between the fibers after squeezing, and in the subsequent impregnation step, alkali liquor is easy to permeate and impregnate, so that the impregnation uniformity is further improved.
(4) Alkali liquor impregnation: soaking the apocynum venetum pulp subjected to primary squeezing in 140g/l NaOH soaking solution with the concentration of 100-30 ℃, wherein the soaking temperature is 20-30 ℃, the soaking time is 30-50 minutes, and the hemicellulose concentration of the soaking solution is less than 20 g/l;
preferably, an auxiliary agent liquid is added in the impregnation step, and the addition amount of the auxiliary agent liquid is 5-8% of the impregnation alkali liquor; the reaction performance of the pulp is further improved, and the degradation of the hemp pulp in the subsequent steps is reduced; compared with cotton pulp and wood pulp, the polymerization degree of the apocynum pulp is easier to degrade after reaching certain conditions; if the cellulose activation is carried out in the early stage without control, the hemp pulp is degraded too violently in the subsequent steps, and finally the fiber strength is lower;
the auxiliary agent liquid comprises the following components: OS-406, dibutyl hydroxy toluene, ethanol, sodium carbonate and deionized water;
the OS-406 is a high molecular weight polyether surfactant solution sold by Guangzhou New Material science and technology Co., Ltd, and has a pH value of 7-9, an HLB value of 17-18, a viscosity of 600-800 mPa.S (25 ℃), and a surface tension of 20-23 mN/m;
the auxiliary agent liquid comprises the following components in parts by weight: 3-6 parts of OS-406, 2-3 parts of dibutyl hydroxy toluene, 3-5 parts of ethanol, 1-2 parts of sodium carbonate and 45-50 parts of deionized water.
The addition of the auxiliary agent liquid can obviously improve the anti-mite and antibacterial agent emission performance and infrared emission rate of the cellulose fiber prepared by the method, and simultaneously further improve the reaction performance of the pulp, wherein the reaction performance can be improved by 5-10%; meanwhile, the oxidative degradation of the hemp pulp liquid in the subsequent steps can be prevented from being aggravated; and after the impregnation is finished, performing a secondary pressing step.
(5) Secondary squeezing: after the impregnation is finished, performing secondary pressing, wherein the secondary pressing temperature is 75-80 ℃, and the pressing multiple is 2.1-2.5; in the secondary squeezing step, residual hydrogen peroxide, alkali liquor and hemicellulose can be removed by rapid squeezing, and simultaneously the content of alpha-cellulose in the fibrilia is further improved, and the reaction performance is improved;
through twice squeezing, the content of hemicellulose in the pulp is obviously reduced, the purity of alpha fiber is further improved, and the fiber strength is improved; meanwhile, the addition amount of carbon disulfide in the yellowing step can be greatly reduced, the cost is reduced, and the average cost per ton is reduced by about 10-20%; through the combination of the processes, the purity of alpha cellulose in the pulp after squeezing is improved by 3-5% compared with that of common alkali cellulose.
(6) Aging: the aging temperature is 28-32 ℃, the aging time is 2.2-3 hours, and the polymerization degree of the fiber after polymerization reduction is controlled to be 500-600; the ageing is a long-time process step in the traditional cellulose fiber process; in the invention, the cellulose activation step is carried out at the initial stage of the process, so that the aging time is reduced, the production efficiency is improved, the efficiency is improved by more than 20 percent compared with the common production process, and meanwhile, the aging time is shortened, so that the process adjustment is matched, and the damage to fibrilia is reduced;
after the aging step, performing an alkali liquor dissolving step to prepare alkali cellulose; in the step of alkali solution, the concentration of the alkali solution is 160-175 g/L.
(7) Preparing a bluish dogbane cellulose sulfonate solution: preparing a jute pulp cellulose sulfonate solution: the addition amount of the carbon disulfide is 22-26% of the content of alpha-cellulose in the aged alkali cellulose; the purity of the alpha fiber is further improved, the addition amount of carbon disulfide in the yellowing step is greatly reduced, and the cost is reduced by about 5-10%; the reaction time in the step of preparing the cellulose sulfonate solution is controlled for 30-40 min; the initial temperature in the preparation step of the cellulose sulfonate solution is controlled to be 22-25 ℃; controlling the terminal temperature to be 26-28 ℃ in the step of preparing the cellulose sulfonate solution to prepare the apocynum venetum viscose; in the reaction process of the carbon disulfide and the alkali cellulose, if the yellowing temperature rises, the yellowing reaction is accelerated, the cellulose oxidative cracking speed is accelerated, and the polymerization degree is obviously reduced, so that proper temperature and time need to be controlled.
Preparation of protein dissolving solution
(1) Adding CHAPS, glycerol and thiourea into deionized water, stirring and dissolving to obtain a CHAPS solution;
adding 2-5% of CHAPS into the CHAPS solution; the temperature of the deionized water is 60-70 ℃; then adding glycerol and thiourea into the solution, and slowly stirring for dissolving; the amount of the added glycerol is 3-6% of the mass of the solution; the adding amount of thiourea is 10-15% of the mass of the solution.
(2) Adding animal colloidal protein powder into the solution prepared in the step (1), stirring and immersing, and then preparing a protein solution by ultrasonic dissolution, alkali addition and heat preservation; the animal colloidal protein powder is one or more of whey protein, puffed feather powder and animal hair powder;
the adding amount of the animal colloidal protein powder is 15-25% of the weight of the CHAPS solution in the step (1);
in the ultrasonic dissolution, the ultrasonic frequency is 100-120 kHz; the ultrasonic power is 50-80W; the ultrasonic temperature is 40-50 ℃; ultrasonic dissolving for 5-10 min; ultrasonic frequency is 2-3 times;
the added alkali is sodium hydroxide; the amount of the added alkali is 20-30% of the mass of the protein powder; the purpose of adding sodium hydroxide can ensure that the prepared protein dissolving solution is better fused with the apocynum venetum cellulose sulfonate solution, thereby achieving better spinning effect; meanwhile, the dissolving speed of the animal colloidal protein is improved;
the heat preservation time is 20-30min, and a protein solution is prepared after heat preservation;
the protein dissolving solution prepared by the method keeps the natural connection and conformation of protein, reduces the elongation of fiber, greatly shortens the preparation time of the protein dissolving solution, improves the spinnability of the fiber, prevents a spinning nozzle from being blocked and improves the production efficiency by 4 to 5 times.
Mixing
Adding the prepared protein solution accounting for 3-10% of the content of the alpha cellulose in the viscose into the prepared apocynum cellulose sulfonate viscose stock solution by using pre-spinning injection equipment according to the effective component to prepare a blended spinning stock solution.
Fourthly, spinning
Filtering and defoaming the spinning solution, and then entering a spinning process; the defoaming adopts a continuous and rapid defoaming method, and the defoaming vacuum degree is less than or equal to-0.1 Mpa;
the filtration adopts a three-way filtration mode, the aperture of a first-way filtration filter screen is 15-25 mu m, and ions and mechanical impurities are removed; removing the micro-particle particles from the second filter screen with the aperture of 10-15 μm; the aperture of the three filter screens is 5-10 μm, so as to prevent the newly added impurities from blocking the spinning jet;
the spinning solution enters a spinneret assembly after passing through a curved tube and a filter, and the spinning solution forms tows through the spinneret assembly and enters a spinning bath; in order to further improve the breaking strength of the prepared fibroin composite cellulose fiber and improve the softness of the fiber, the spinning bath is reset; the spinning bath is divided into a first bath, a second bath and a third bath;
the one-bath composition comprises: 70-80g/l of sulfuric acid, 220-260g/l of sodium sulfate and one bath temperature of 30-50 ℃; the drawing rate after one bath is 30-35%;
the two bath components comprise sulfuric acid with the concentration of 40-50 g/l; the drafting rate after the second bath is 50-60%; the temperature of the second bath is 65-75 ℃;
the three bath components comprise sulfuric acid with the concentration of 10-20 g/l; the drafting rate after three baths is 20-30%, and the temperature of the three baths is 60-70 ℃;
through the adjusted drafting, zinc sulfate is removed, so that zinc-free spinning is realized, the environmental protection pressure is reduced, meanwhile, the component contents, the temperature and the drafting rate of the first bath, the second bath and the third bath are adjusted, the crystal structure of the fiber is changed, the breaking strength of the fiber is greatly improved, and the softness of the prepared animal colloidal protein composite apocynum venetum cellulose fiber is improved;
in the second bath, a denaturant is preferably added; the denaturant is one or more of LS-6 and HB-652;
the denaturant is produced by Shenyang Haobo industry Co.Ltd; the concentration of the denaturant in the acid bath is 10-25 mg/L; the denaturant can reduce the interfacial tension between the viscose and the solution, disperse the precipitate mainly containing sulfur in the spinning bath, reduce scaling and spinning nozzle blockage, prolong the head changing period, improve the spinnability and greatly improve the fiber luster.
Due to the adoption of the technical scheme, the invention achieves the technical effects that:
1. the cellulose fiber prepared by the invention has good glossiness, and the protein in the fiber keeps natural connection and conformation, so that the prepared cellulose fiber has high fiber strength and low elongation, and the animal colloidal protein in the fiber is not easy to run off;
2. the cellulose fiber prepared by the invention meets the following indexes: the dry breaking strength is more than or equal to 3.5cN/dtex, the wet breaking strength is more than or equal to 2.8cN/dtex, the animal colloidal protein content is more than or equal to 3%, the dry breaking elongation is 11-13%, the wet breaking elongation is 11-14%, the fineness deviation rate is less than or equal to 1.5%, the linear density deviation rate is less than or equal to +/-3%, the residual sulfur content is less than or equal to 7mg/100g, the defects are less than or equal to 3mg/100g, the length-doubled fiber is less than or equal to 0.5mg/100mg, the length deviation rate is less than or equal to +/-2%, and the whiteness;
3. the fabric prepared by adopting the animal colloidal protein composite apocynum venetum cellulose fiber prepared by the invention is prepared according to GB-T20944.3-2008 part 3 of evaluation of antibacterial property of textile: according to the stipulation of the oscillation method, the antibacterial performance of the cellulose fiber prepared by the invention is detected by the national ecological textile quality supervision and inspection center, the inhibition rate of staphylococcus aureus reaches 97.0-98.3%, the inhibition rate of escherichia coli reaches 99.1-99.6%, and the inhibition rate of candida albicans reaches 99.2-99.8%;
4. the close-fitting fabric made of the cellulose fibers has good anti-radiation and far infrared emission performances, and the far infrared emission rate of the animal colloidal protein composite apocynum venetum cellulose fibers is 95.6-99.1% by adopting FZ/T64010 standard detection; due to excellent infrared emissivity, the manufactured clothes have the characteristics of heat retention of 2.5-3 times that of all-cotton underwear below 8 ℃, air permeability of 3.5 times that of pure cotton fabrics above 21 ℃, and unique 'warm in winter and cool in summer';
5. the close-fitting fabric prepared from the cellulose fiber has good mite removing performance, and the mite removing rate of the animal colloidal protein composite apocynum venetum cellulose fiber is 98.5-99.6% by adopting the GBT 24253-2009 standard for detection;
6. because the dry elongation at break and the wet elongation at break of the cellulose fiber prepared by the invention are lower, yarns, fabrics and clothes made of the cellulose fiber are hardly deformed and shrunk after being washed and used, and have good deformation resistance;
7. the invention adopts the apocynum venetum pulp, the prepared fiber keeps the natural characteristics of the apocynum venetum and has the functions of resisting radiation, emitting far infrared rays, resisting bacteria and delaying senility; the animal protein contained in the fiber can play a role of supplementing amino acid to a human body, the prepared fiber is smooth and glossy, and meanwhile, the prepared cellulose fiber has the characteristics of softness and fineness;
8. the cellulose fiber prepared by the method has good ultraviolet resistance, and can be used for manufacturing a close-fitting ultraviolet-resistant lining and the like.
Detailed Description
Embodiment 1 a method for preparing animal colloidal protein composite apocynum venetum cellulose fiber, comprising the following steps:
firstly, preparing apocynum venetum viscose liquid
(1) Crushing the apocynum venetum pulp into pulp porridge with the concentration of 400g/L by a crusher;
(2) activating cellulose: adding hydrogen peroxide into the prepared apocynum venetum slurry porridge, and reacting for 30-50min after the slurry porridge is heated; the concentration of the hydrogen peroxide in the apocynum pulp porridge is 20 g/L; heating the slurry porridge to 50 ℃;
adding an activating agent dz-01 in the process of activating the cellulose; the concentration of the activating agent in the paste is 1 g/L; the activating agent dz-01 is produced by Zibobi biological enzyme, Inc.;
(3) primary squeezing: the squeezing temperature is 26 ℃, and the squeezing multiple is 1.6 times;
(4) alkali liquor impregnation: soaking the apocynum venetum pulp subjected to primary squeezing in 100g/l NaOH soaking solution at the soaking temperature of 20 ℃ for 30 minutes, wherein the hemicellulose concentration of the soaking solution is less than 20 g/l;
the auxiliary liquid comprises the following components: OS-406, dibutyl hydroxy toluene, ethanol, sodium carbonate and deionized water;
OS-406, which is a high molecular weight polyether surfactant solution sold by Guangzhou New Material science and technology Co., Ltd, has a pH value of 7-9, an HLB value of 17-18, a viscosity of 600-800 mPa.S (25 ℃), and a surface tension of 20-23 mN/m; in the auxiliary agent liquid, the components are specifically as follows according to parts by weight: 3 parts of OS-406, 2 parts of dibutyl hydroxy toluene, 3 parts of ethanol, 2 parts of sodium carbonate and 45 parts of deionized water;
(5) secondary squeezing: after the impregnation is finished, secondary pressing is carried out, wherein the temperature of the secondary pressing is 75 ℃, and the pressing multiple is 2.1;
(6) aging: the aging temperature is 28 ℃, the aging time is 2.2 hours, and the polymerization degree of the fiber after polymerization reduction is controlled to be 500; after the aging step, performing an alkali liquor dissolving step to prepare alkali cellulose; in the step of alkali liquor solution, the concentration of the alkali liquor is 160 g/L;
(7) preparing a bluish dogbane cellulose sulfonate solution: the adding amount of the carbon disulfide is 22 percent of the content of alpha-cellulose in the aged alkali cellulose; the reaction time in the preparation step of the cellulose sulfonate solution is controlled for 30 min; the initial temperature in the preparation step of the cellulose sulfonate solution is controlled to be 22 ℃; and in the step of preparing the cellulose sulfonate solution, the terminal temperature is controlled to be 27 ℃, and the apocynum venetum viscose solution is prepared.
Preparation of protein dissolving solution
(1) Adding CHAPS, glycerol and thiourea into deionized water, stirring and dissolving to obtain a CHAPS solution; adding 2% of CHAPS into the CHAPS solution; the temperature of the deionized water is 60 ℃; then adding glycerol and thiourea into the solution, and slowly stirring for dissolving; the amount of the added glycerol is 3 percent of the mass of the solution; the adding amount of thiourea is 11% of the mass of the solution;
(2) adding animal colloidal protein powder into the solution prepared in the step (1), stirring and immersing, and then preparing a protein solution by ultrasonic dissolution, alkali addition and heat preservation; the animal colloidal protein powder is whey protein;
the adding amount of whey is 15% of the weight of the CHAPS solution in the step (1);
in ultrasonic dissolution, the ultrasonic frequency is 100 kHz; the ultrasonic power is 50W; the ultrasonic temperature is 40 ℃; ultrasonic dissolving time is 10 min; the ultrasonic frequency is 2 times;
the added alkali is sodium hydroxide; the amount of the added alkali is 22 percent of the mass of the protein powder; keeping the temperature for 20min, and keeping the temperature to obtain a protein solution;
mixing
In the prepared apocynum venetum cellulose sulfonate viscose stock solution, the prepared protein dissolving solution accounting for 3 percent of the content of the alpha cellulose in the viscose is added by utilizing injection equipment before spinning to prepare blended spinning stock solution.
Fourthly, spinning
Filtering and defoaming the spinning solution, and then entering a spinning process; the defoaming adopts a continuous and rapid defoaming method, and the defoaming vacuum degree is less than or equal to-0.1 Mpa;
the filtration adopts a three-way filtration mode, the aperture of a first filtration filter screen is 15 mu m, and ions and mechanical impurities are removed; removing micro-particle particles from the second filter screen with the aperture of 10 mu m; the aperture of the three filter screens is 5 mu m, so that the newly added impurities are prevented from blocking a spinning nozzle; in the spinning procedure, the spinning bath is divided into a first bath, a second bath and a third bath;
one bath composition comprises: 70g/l of sulfuric acid, 225g/l of sodium sulfate and 35 ℃ of one bath temperature; the drawing rate after one bath is 31 percent;
the second bath component included sulfuric acid at a concentration of 41 g/l; the drawing rate after the second bath is 51 percent; the temperature of the second bath is 68 ℃;
the three bath components comprise sulfuric acid with the concentration of 12 g/l; the drafting rate after three baths is 23 percent, and the temperature of the three baths is 60 ℃;
in the second bath, a denaturant LS-6 is added; (ii) a
The denaturant is produced by Shenyang Haobo industry Co.Ltd; the concentration of the denaturant in the acid bath is 10 mg/L;
embodiment 2 a method for preparing animal colloidal protein composite apocynum venetum cellulose fiber, comprising the following steps:
firstly, preparing apocynum venetum viscose liquid
(1) Crushing the apocynum venetum pulp into pulp porridge with the concentration of 450g/L by a crusher;
(2) activating cellulose: adding hydrogen peroxide into the prepared apocynum venetum slurry porridge, and reacting for 35min after the slurry porridge is heated; the concentration of hydrogen peroxide in the apocynum pulp porridge is 24 g/L; heating the slurry porridge to 55 ℃; adding an activating agent dz-01 in the process of activating the cellulose; the concentration of the activating agent in the paste is 3 g/L;
(3) primary squeezing: the squeezing temperature is 28 ℃, and the squeezing multiple is 1.9 times;
(4) alkali liquor impregnation: soaking the apocynum venetum pulp subjected to primary squeezing in 140g/l NaOH soaking solution with the concentration of 100-;
in the dipping step, an auxiliary agent liquid is added, and the addition amount of the auxiliary agent liquid is 5 percent of the dipping alkali liquor; the auxiliary liquid comprises the following components: OS-406, dibutyl hydroxy toluene, ethanol, sodium carbonate and deionized water;
OS-406, pH 7.5, HLB 17, viscosity 650 mPaS (25 ℃), surface tension 22 mN/m; in the auxiliary agent liquid, the components are specifically as follows according to parts by weight: 5 parts of OS-406, 2 parts of dibutyl hydroxy toluene, 5 parts of ethanol, 1 part of sodium carbonate and 45 parts of deionized water.
(5) Secondary squeezing: the secondary pressing temperature is 76 ℃, and the pressing multiple is 2.2;
(6) aging: the aging temperature is 30 ℃, the aging time is 2.8 hours, and the polymerization degree of the fiber after polymerization reduction is controlled to be 500; after the aging step, performing an alkali liquor dissolving step to prepare alkali cellulose; in the step of alkali liquor solution, the concentration of the alkali liquor is 170 g/L.
(7) Preparing a bluish dogbane cellulose sulfonate solution: the adding amount of the carbon disulfide is 23 percent of the content of alpha-cellulose in the aged alkali cellulose; the reaction time in the preparation step of the cellulose sulfonate solution is controlled for 36 min; the initial temperature in the preparation step of the cellulose sulfonate solution is controlled to be 24 ℃; and in the step of preparing the cellulose sulfonate solution, the terminal temperature is controlled at 28 ℃, and the apocynum venetum viscose is prepared.
Preparation of protein dissolving solution
(1) Adding CHAPS, glycerol and thiourea into deionized water, stirring and dissolving to obtain a CHAPS solution;
adding 3% of CHAPS into the CHAPS solution; the temperature of the deionized water is 65 ℃; then adding glycerol and thiourea into the solution, and slowly stirring for dissolving; the amount of the added glycerol is 4 percent of the mass of the solution; the adding amount of thiourea is 13 percent of the mass of the solution;
(2) adding animal colloidal protein powder into the solution prepared in the step (1), stirring and immersing, and then preparing a protein solution by ultrasonic dissolution, alkali addition and heat preservation; the animal colloidal protein is puffed feather powder; the adding amount of the puffed feather powder is 20 percent of the mass of the CHAPS solution in the step (1);
in ultrasonic dissolution, the ultrasonic frequency is 120 kHz; the ultrasonic power is 65W; the ultrasonic temperature is 45 ℃; ultrasonic dissolving time is 8 min; the ultrasonic frequency is 2 times;
keeping the temperature for 25min, and keeping the temperature to obtain a protein solution;
mixing
In the prepared apocynum venetum cellulose sulfonate viscose stock solution, the prepared protein dissolving solution accounting for 7 percent of the content of the alpha cellulose in the viscose is added according to the effective component by using injection equipment before spinning to prepare blended spinning stock solution.
Fourthly, spinning
Filtering and defoaming the spinning solution, and then entering a spinning process; the defoaming adopts a continuous and rapid defoaming method, and the defoaming vacuum degree is less than or equal to-0.1 Mpa;
the filtration adopts a three-way filtration mode, the aperture of a first-way filtration filter screen is 21 mu m, and ions and mechanical impurities are removed; removing micro-particle particles from the second filter screen with the aperture of 10 mu m; the aperture of the three filter screens is 5 mu m, so that the newly added impurities are prevented from blocking a spinning nozzle;
the spinning solution enters a spinneret assembly after passing through a curved tube and a filter, and the spinning solution forms tows through the spinneret assembly and enters a spinning bath; the spinning bath is divided into a first bath, a second bath and a third bath;
one bath composition comprises: 78g/l of sulfuric acid, 245g/l of sodium sulfate and 40 ℃ of one bath temperature; the drawing rate after one bath is 32 percent;
the second bath component comprises sulfuric acid with a concentration of 45 g/l; the draft ratio after the second bath is 55 percent; the temperature of the second bath is 70 ℃;
the three bath components comprise sulfuric acid with the concentration of 15 g/l; the drafting rate after three baths is 25 percent, and the temperature of the three baths is 66 ℃;
in the second bath, a denaturant is added; the denaturant is HB-652;
the denaturant is produced by Shenyang Haobo industry Co.Ltd; the concentration of the denaturant in the acid bath is 22 mg/L;
embodiment 3 a method for preparing animal colloidal protein composite apocynum venetum cellulose fiber, comprising the following steps:
firstly, preparing apocynum venetum viscose liquid
(1) Crushing the apocynum venetum pulp into pulp porridge with the concentration of 450g/L by a crusher;
(2) activating cellulose: adding hydrogen peroxide into the prepared apocynum venetum slurry porridge, and reacting for 45min after the slurry porridge is heated; the concentration of hydrogen peroxide in the apocynum pulp porridge is 30 g/L; heating the slurry porridge to 60 ℃; adding an activating agent dz-01 in the process of activating the cellulose; the concentration of the activating agent in the slurry is 2 g/L;
(3) primary squeezing: the squeezing temperature is 32 ℃, and the squeezing multiple is 2.3 times;
(4) alkali liquor impregnation: soaking the apocynum venetum pulp subjected to primary squeezing in NaOH soaking liquid with the concentration of 140g/l at the temperature of 30 ℃ for 50 minutes, wherein the hemicellulose concentration of the soaking liquid is less than 20 g/l;
in the dipping step, an auxiliary agent liquid is added, and the addition amount of the auxiliary agent liquid is 8 percent of the dipping alkali liquor; the auxiliary liquid comprises the following components: OS-406, dibutyl hydroxy toluene, ethanol, sodium carbonate and deionized water;
the OS-406 is a high molecular weight polyether surfactant solution sold by Guangzhou New Material science and technology Co., Ltd, and has a pH value of 7-9, an HLB value of 17-18, a viscosity of 600-800 mPa.S (25 ℃), and a surface tension of 20-23 mN/m;
in the auxiliary agent liquid, the components are specifically as follows according to parts by weight: 6 parts of OS-406, 3 parts of dibutyl hydroxy toluene, 5 parts of ethanol, 2 parts of sodium carbonate and 50 parts of deionized water;
(5) secondary squeezing: the secondary pressing temperature is 80 ℃, and the pressing multiple is 2.5;
(6) aging: the aging temperature is 32 ℃, the aging time is 3 hours, and the polymerization degree of the fiber after polymerization reduction is controlled to be 600;
after the aging step, performing an alkali liquor dissolving step to prepare alkali cellulose; in the step of alkali liquor solution, the concentration of alkali liquor is 175 g/L.
(7) Preparing a bluish dogbane cellulose sulfonate solution: the addition amount of the carbon disulfide is 6 percent of the content of alpha-cellulose in the aged alkali cellulose; the reaction time in the preparation step of the cellulose sulfonate solution is controlled for 40 min; the initial temperature in the preparation step of the cellulose sulfonate solution is controlled to be 25 ℃; and in the step of preparing the cellulose sulfonate solution, the terminal temperature is controlled at 28 ℃, and the apocynum venetum viscose is prepared.
Preparation of protein dissolving solution
(1) Adding CHAPS, glycerol and thiourea into deionized water, stirring and dissolving to obtain a CHAPS solution;
adding 5% of CHAPS into the CHAPS solution; the temperature of the deionized water is 70 ℃; then adding glycerol and thiourea into the solution, and slowly stirring for dissolving; the amount of the added glycerol is 6 percent of the mass of the solution; the adding amount of thiourea is 13 percent of the mass of the solution;
(2) adding animal colloidal protein powder into the solution prepared in the step (1), stirring and immersing, and then preparing a protein solution by ultrasonic dissolution, alkali addition and heat preservation; the animal colloidal protein powder is animal hair powder;
the adding amount of the animal hair powder is 25 percent of the weight of the CHAPS solution in the step (1);
in ultrasonic dissolution, the ultrasonic frequency is 120 kHz; the ultrasonic power is 80W; the ultrasonic temperature is 50 ℃; ultrasonic dissolving time is 10 min; the ultrasonic frequency is 3 times;
the added alkali is sodium hydroxide; the amount of the added alkali is 30 percent of the mass of the protein powder; the heat preservation time is 30min, and a protein solution is prepared after heat preservation;
mixing
In the prepared apocynum venetum cellulose sulfonate viscose stock solution, the prepared protein dissolving solution accounting for 10 percent of the content of the alpha cellulose in the viscose is added according to the effective component by using injection equipment before spinning to prepare blended spinning stock solution.
Fourthly, spinning
Filtering and defoaming the spinning solution, and then entering a spinning process; the defoaming adopts a continuous and rapid defoaming method, and the defoaming vacuum degree is less than or equal to-0.1 Mpa;
the filtration adopts a three-way filtration mode, the aperture of a first filtration filter screen is 15 mu m, and ions and mechanical impurities are removed; removing micro-particle particles from the second filter screen with the aperture of 15 mu m; the aperture of the three filter screens is 10 mu m, so that the newly added impurities are prevented from blocking a spinning nozzle;
the spinning solution enters a spinneret assembly after passing through a curved tube and a filter, and the spinning solution forms tows through the spinneret assembly and enters a spinning bath; the spinning bath is divided into a first bath, a second bath and a third bath;
one bath composition comprises: 80g/l of sulfuric acid, 260g/l of sodium sulfate and 50 ℃ of one bath temperature; the drawing rate after one bath is 35 percent;
the second bath component comprises sulfuric acid with the concentration of 50 g/l; the drawing rate after the second bath is 60 percent; the temperature of the second bath is 75 ℃;
the three bath components comprise sulfuric acid with the concentration of 20 g/l; the drawing rate after three baths is 30 percent, and the temperature of the three baths is 60 ℃;
in the second bath, a denaturant is added; the denaturant is a mixture of LS-6 and HB-652; the mass ratio of LS-6 to HB-652 in the denaturant is 1.2: 2;
the concentration of the denaturant in the acid bath was 25 mg/L.
Comparative example 4 a method for preparing an animal colloidal protein composite apocynum venetum cellulose fiber, comprising the steps of:
firstly, preparing apocynum venetum viscose liquid
(1) Crushing the apocynum venetum pulp into pulp porridge with the concentration of 450g/L by a crusher;
(2) activating cellulose: adding hydrogen peroxide into the prepared apocynum venetum slurry porridge, and reacting for 45min after the slurry porridge is heated; the concentration of hydrogen peroxide in the apocynum pulp porridge is 30 g/L; heating the slurry porridge to 60 ℃; adding an activating agent dz-01 in the process of activating the cellulose; the concentration of the activating agent in the slurry is 1 g/L;
(3) primary squeezing: the squeezing temperature is 32 ℃, and the squeezing multiple is 2.3 times;
(4) alkali liquor impregnation: soaking the apocynum venetum pulp subjected to primary squeezing in NaOH soaking liquid with the concentration of 140g/l at the temperature of 30 ℃ for 50 minutes, wherein the hemicellulose concentration of the soaking liquid is less than 20 g/l;
(5) secondary squeezing: the secondary pressing temperature is 80 ℃, and the pressing multiple is 2.5;
(6) aging: the aging temperature is 32 ℃, the aging time is 3 hours, and the polymerization degree of the fiber after polymerization reduction is controlled to be 600;
after the aging step, performing an alkali liquor dissolving step to prepare alkali cellulose; in the step of alkali liquor solution, the concentration of alkali liquor is 175 g/L.
(7) Preparing a bluish dogbane cellulose sulfonate solution: the addition amount of the carbon disulfide is 6 percent of the content of alpha-cellulose in the aged alkali cellulose; the reaction time in the preparation step of the cellulose sulfonate solution is controlled for 40 min; the initial temperature in the preparation step of the cellulose sulfonate solution is controlled to be 25 ℃; and in the step of preparing the cellulose sulfonate solution, the terminal temperature is controlled at 28 ℃, and the apocynum venetum viscose is prepared.
Preparation of protein dissolving solution
(1) Adding CHAPS, glycerol and thiourea into deionized water, stirring and dissolving to obtain a CHAPS solution;
adding 5% of CHAPS into the CHAPS solution; the temperature of the deionized water is 70 ℃; then adding glycerol and thiourea into the solution, and slowly stirring for dissolving; the amount of the added glycerol is 6 percent of the mass of the solution; the adding amount of thiourea is 13 percent of the mass of the solution;
(2) adding animal colloidal protein powder into the solution prepared in the step (1), stirring and immersing, and then preparing a protein solution by ultrasonic dissolution, alkali addition and heat preservation; the animal colloidal protein powder is animal hair powder;
the adding amount of the animal hair powder is 25 percent of the weight of the CHAPS solution in the step (1);
in ultrasonic dissolution, the ultrasonic frequency is 120 kHz; the ultrasonic power is 80W; the ultrasonic temperature is 50 ℃; ultrasonic dissolving time is 10 min; the ultrasonic frequency is 3 times;
the added alkali is sodium hydroxide; the amount of the added alkali is 30 percent of the mass of the protein powder; the heat preservation time is 30min, and a protein solution is prepared after heat preservation;
mixing
In the prepared apocynum venetum cellulose sulfonate viscose stock solution, the prepared protein dissolving solution accounting for 10 percent of the content of the alpha cellulose in the viscose is added according to the effective component by using injection equipment before spinning to prepare blended spinning stock solution.
Fourthly, spinning
Filtering and defoaming the spinning solution, and then entering a spinning process; the defoaming adopts a continuous and rapid defoaming method, and the defoaming vacuum degree is less than or equal to-0.1 Mpa;
the filtration adopts a three-way filtration mode, the aperture of a first filtration filter screen is 15 mu m, and ions and mechanical impurities are removed; removing micro-particle particles from the second filter screen with the aperture of 15 mu m; the aperture of the three filter screens is 10 mu m, so that the newly added impurities are prevented from blocking a spinning nozzle;
the spinning solution enters a spinneret assembly after passing through a curved tube and a filter, and the spinning solution forms tows through the spinneret assembly and enters a spinning bath; the spinning bath is divided into a first bath, a second bath and a third bath;
one bath composition comprises: 80g/l of sulfuric acid, 260g/l of sodium sulfate and 50 ℃ of one bath temperature; the drawing rate after one bath is 35 percent;
the second bath component comprises sulfuric acid with the concentration of 50 g/l; the drawing rate after the second bath is 60 percent; the temperature of the second bath is 75 ℃;
the three bath components comprise sulfuric acid with the concentration of 20 g/l; the drawing rate after three baths is 30 percent, and the temperature of the three baths is 60 ℃;
in the second bath, a denaturant is added; the denaturant is a mixture of LS-6 and HB-652; the mass ratio of LS-6 to HB-652 in the denaturant is 1.2: 2;
the concentration of the denaturant in the acid bath was 25 mg/L.
Comparative example 5 a method for preparing an animal colloidal protein composite apocynum venetum cellulose fiber, comprising the steps of:
firstly, preparing apocynum venetum viscose liquid
(1) Crushing the apocynum venetum pulp into pulp porridge with the concentration of 450g/L by a crusher;
(2) activating cellulose: adding hydrogen peroxide into the prepared apocynum venetum slurry porridge, and reacting for 45min after the slurry porridge is heated; the concentration of hydrogen peroxide in the apocynum pulp porridge is 30 g/L; heating the slurry porridge to 60 ℃; adding an activating agent dz-01 in the process of activating the cellulose; the concentration of the activating agent in the slurry is 1 g/L;
(3) primary squeezing: the squeezing temperature is 32 ℃, and the squeezing multiple is 2.3 times;
(4) alkali liquor impregnation: soaking the apocynum venetum pulp subjected to primary squeezing in NaOH soaking liquid with the concentration of 140g/l at the temperature of 30 ℃ for 50 minutes, wherein the hemicellulose concentration of the soaking liquid is less than 20 g/l;
in the dipping step, an auxiliary agent liquid is added, and the addition amount of the auxiliary agent liquid is 8 percent of the dipping alkali liquor; the auxiliary liquid comprises the following components: OS-406, dibutyl hydroxy toluene, ethanol, sodium carbonate and deionized water;
the OS-406 is a high molecular weight polyether surfactant solution sold by Guangzhou New Material science and technology Co., Ltd, and has a pH value of 7-9, an HLB value of 17-18, a viscosity of 600-800 mPa.S (25 ℃), and a surface tension of 20-23 mN/m;
in the auxiliary agent liquid, the components are specifically as follows according to parts by weight: 6 parts of OS-406, 3 parts of dibutyl hydroxy toluene, 5 parts of ethanol, 2 parts of sodium carbonate and 50 parts of deionized water;
(5) secondary squeezing: the secondary pressing temperature is 80 ℃, and the pressing multiple is 2.5;
(6) aging: the aging temperature is 32 ℃, the aging time is 3 hours, and the polymerization degree of the fiber after polymerization reduction is controlled to be 600;
after the aging step, performing an alkali liquor dissolving step to prepare alkali cellulose; in the step of alkali liquor solution, the concentration of alkali liquor is 175 g/L.
(7) Preparing a bluish dogbane cellulose sulfonate solution: the addition amount of the carbon disulfide is 6 percent of the content of alpha-cellulose in the aged alkali cellulose; the reaction time in the preparation step of the cellulose sulfonate solution is controlled for 40 min; the initial temperature in the preparation step of the cellulose sulfonate solution is controlled to be 25 ℃; and in the step of preparing the cellulose sulfonate solution, the terminal temperature is controlled at 28 ℃, and the apocynum venetum viscose is prepared.
Preparation of protein dissolving solution
(1) Adding CHAPS, glycerol and thiourea into deionized water, stirring and dissolving to obtain a CHAPS solution;
adding 5% of CHAPS into the CHAPS solution; the temperature of the deionized water is 70 ℃; then adding glycerol and thiourea into the solution, and slowly stirring for dissolving; the amount of the added glycerol is 6 percent of the mass of the solution; the adding amount of thiourea is 13 percent of the mass of the solution;
(2) adding animal colloidal protein powder into the solution prepared in the step (1), stirring and immersing, and then preparing a protein solution by ultrasonic dissolution, alkali addition and heat preservation; the animal colloidal protein powder is animal hair powder;
the adding amount of the animal hair powder is 25 percent of the weight of the CHAPS solution in the step (1);
in ultrasonic dissolution, the ultrasonic frequency is 120 kHz; the ultrasonic power is 80W; the ultrasonic temperature is 50 ℃; ultrasonic dissolving time is 10 min; the ultrasonic frequency is 3 times;
the added alkali is sodium hydroxide; the amount of the added alkali is 30 percent of the mass of the protein powder; the heat preservation time is 30min, and a protein solution is prepared after heat preservation;
mixing
In the prepared apocynum venetum cellulose sulfonate viscose stock solution, the prepared protein dissolving solution accounting for 10 percent of the content of the alpha cellulose in the viscose is added according to the effective component by using injection equipment before spinning to prepare blended spinning stock solution.
Fourthly, spinning
Filtering and defoaming the spinning solution, and then entering a spinning process; the defoaming adopts a continuous and rapid defoaming method, and the defoaming vacuum degree is less than or equal to-0.1 Mpa;
the filtration adopts a three-way filtration mode, the aperture of a first filtration filter screen is 15 mu m, and ions and mechanical impurities are removed; removing micro-particle particles from the second filter screen with the aperture of 15 mu m; the aperture of the three filter screens is 10 mu m, so that the newly added impurities are prevented from blocking a spinning nozzle;
the spinning solution enters a spinneret assembly after passing through a curved tube and a filter, and the spinning solution forms tows through the spinneret assembly and enters a spinning bath; the spinning bath comprises the following components: 80g/l of sulfuric acid, 260g/l of sodium sulfate and 50 ℃ of one bath temperature; the draft was 35%.
The animal colloidal protein composite apocynum venetum cellulose fibers prepared in the examples 1 to 3 and the comparative examples 4 and 5 of the invention have the following relevant indexes, which are shown in Table 1
TABLE 1
As can be seen from the table 1, the dry breaking strength of the animal colloidal protein composite apocynum venetum cellulose fiber prepared by the invention is more than or equal to 3.5cN/dtex, the wet breaking strength is more than or equal to 2.8cN/dtex, the dry breaking elongation is 11-13%, and the wet breaking elongation is 11-14%; the fabric prepared by adopting the animal colloidal protein composite apocynum venetum cellulose fiber prepared by the invention is prepared according to GB-T20944.3-2008 part 3 of evaluation of antibacterial property of textile: according to the stipulation of the oscillation method, the antibacterial performance of the cellulose fiber prepared by the invention is detected by the national ecological textile quality supervision and inspection center, the inhibition rate of staphylococcus aureus reaches 97.0-98.3%, the inhibition rate of escherichia coli reaches 99.1-99.6%, and the inhibition rate of candida albicans reaches 99.2-99.8%;
the close-fitting fabric made of the cellulose fibers has good anti-radiation and far infrared emission performances, and the far infrared emission rate of the animal colloidal protein composite apocynum venetum cellulose fibers is 95.6-99.1% by adopting FZ/T64010 standard detection; due to excellent infrared emissivity, the manufactured clothes have the characteristics of heat retention of 2.5-3 times that of all-cotton underwear below 8 ℃, air permeability of 3.5 times that of pure cotton fabrics above 21 ℃, and unique 'warm in winter and cool in summer';
the close-fitting fabric prepared from the cellulose fiber has good mite removing performance, and the mite removing rate of the animal colloidal protein composite apocynum venetum cellulose fiber is 98.5-99.6% by adopting the GBT 24253-2009 standard for detection;
example 3 is the best embodiment of the invention;
meanwhile, comparative example 4 is a basic process using example 3, with only the dipping step changed: without addition of an auxiliary agent liquid, as can be seen from table 1, the cellulose fiber prepared by the method has great influence on the antibacterial performance, far infrared emissivity and anti-mite performance of the cellulose fiber;
comparative example 5 also the basic process of example 3 was used, with only three changes in the spinning bath: the cellulose fibers prepared in comparative example 5 were subjected to coagulation in a primary spinning bath, and as can be seen from table 1, the dry breaking strength and the dry and wet elongation at break were greatly changed.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can still make modifications to the technical solutions described in the foregoing embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
1. A preparation method of animal colloidal protein composite apocynum venetum cellulose fiber is characterized by comprising the following steps: the fiber satisfies: the content of animal colloidal protein is more than or equal to 3 percent, the dry breaking elongation is 11-13 percent, the wet breaking elongation is 11-14 percent, the dry breaking strength is more than or equal to 3.5cN/dtex, the wet breaking strength is more than or equal to 2.8cN/dtex, the fineness deviation rate is less than or equal to 1.5 percent, the residual sulfur content is less than or equal to 7mg/100g, the defects are less than or equal to 3mg/100g, the length-doubled fiber is less than or equal to 0.5mg/100mg, and the whiteness is more than or equal;
the preparation method of the animal colloidal protein composite apocynum venetum cellulose fiber comprises the step of preparing a protein dissolving solution; the preparation method of the protein dissolving solution comprises the following steps: adding CHAPS, glycerol and thiourea into deionized water, stirring and dissolving to obtain CHAPS solution, adding animal colloidal protein powder into the CHAPS solution, stirring, ultrasonically dissolving, adding alkali, and keeping the temperature to obtain protein dissolved solution;
adding 2-5% of CHAPS into the CHAPS solution; the temperature of the deionized water is 60-70 ℃; the amount of the added glycerol is 3-6% of the mass of the solution; the amount of the added thiourea is 10-15% of the mass of the solution;
in the ultrasonic dissolving step, the ultrasonic frequency is 100-120 kHz; the ultrasonic power is 50-80W; the ultrasonic temperature is 40-50 ℃; ultrasonic dissolving for 5-10 min; ultrasonic frequency is 2-3 times; the added alkali is sodium hydroxide; the amount of the added alkali is 20-30% of the mass of the protein powder; the heat preservation time is 20-30min, and the protein solution is prepared after heat preservation.
2. The preparation method of the animal colloidal protein composite apocynum venetum cellulose fiber according to claim 1, characterized by comprising the following steps: the animal colloidal protein powder is one or more of whey protein, puffed feather powder and animal hair powder; the adding amount of the animal colloidal protein powder is 15-25% of the weight of the CHAPS solution.
3. The preparation method of the animal colloidal protein composite apocynum venetum cellulose fiber according to claim 1, characterized by comprising the following steps: the method also comprises a preparation step of preparing the apocynum venetum viscose; the preparation step of the apocynum venetum viscose liquid comprises a cellulose activation step; the cellulose activation step: adding hydrogen peroxide into the prepared apocynum venetum pulp porridge; heating the slurry and reacting for 30-50 min; the concentration of hydrogen peroxide in the apocynum pulp porridge is 20-30 g/L; heating the slurry porridge to 50-60 ℃; adding an activating agent dz-01 in the process of activating the cellulose; the concentration of the activating agent in the slurry porridge is 1-3 g/L.
4. The preparation method of the animal colloidal protein composite apocynum venetum cellulose fiber according to claim 1, characterized by comprising the following steps: the method further comprises a lye impregnation step; the alkali liquor dipping step: soaking the apocynum venetum pulp subjected to primary pressing in 140g/l NaOH soaking solution with the concentration of 100-30 ℃ for 30-50 minutes.
5. The preparation method of the animal colloidal protein composite apocynum venetum cellulose fiber according to claim 4, characterized by comprising the following steps: adding an auxiliary agent liquid in the impregnation step, wherein the addition amount of the auxiliary agent liquid is 5-8% of the impregnation alkali liquor; the auxiliary agent liquid comprises the following components: OS-406, dibutyl hydroxy toluene, ethanol, sodium carbonate and deionized water; the OS-406 is a high molecular weight polyether surfactant solution, the pH value is 7-9, the HLB value is 17-18, the viscosity is 600-800 mPa.S (25 ℃), and the surface tension is 20-23 mN/m; the auxiliary agent liquid comprises the following components in parts by weight: 3-6 parts of OS-406, 2-3 parts of dibutyl hydroxy toluene, 3-5 parts of ethanol, 1-2 parts of sodium carbonate and 45-50 parts of deionized water.
6. The preparation method of the animal colloidal protein composite apocynum venetum cellulose fiber according to claim 1, characterized by comprising the following steps: the method further comprises a spinning step; in the spinning step, the spinning bath is divided into a first bath, a second bath and a third bath; the one-bath composition comprises: 70-80g/l of sulfuric acid, 220-260g/l of sodium sulfate and one bath temperature of 30-50 ℃; the drawing rate after one bath is 30-35%; the two bath components comprise sulfuric acid with the concentration of 40-50 g/l; the drafting rate after the second bath is 50-60%; the temperature of the second bath is 65-75 ℃; the three bath components comprise sulfuric acid with the concentration of 10-20 g/l; the drafting rate after three baths is 20-30%, and the temperature of the three baths is 60-70 ℃.
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