CN111690997A - Multiple mildew-proof composite textile fabric and preparation method thereof - Google Patents
Multiple mildew-proof composite textile fabric and preparation method thereof Download PDFInfo
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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
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
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- D06M2101/06—Vegetal fibres cellulosic
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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Abstract
The invention relates to the technical field of spinning fibers, and discloses a multiple mildew-proof composite textile fabric and a preparation method thereof aiming at the problem that the existing textile fabric is poor in mildew-proof durability, wherein the textile fabric is woven by modified viscose fibers, and the modified viscose fibers are prepared from the following raw materials in parts by weight: 70-80 parts of viscose stock solution, 10-20 parts of modified bamboo fiber, 5-10 parts of mildew-proof polymer and 1-3 parts of lauryl polyoxyethylene ether, and the surface of the prepared spinning fiber is subjected to hydrophobic modification. The invention realizes long-lasting bacteriostatic and mildewproof effects by introducing bacteriostatic functional groups, and achieves multiple bacteriostatic effects by bacteriostatic modification of natural bamboo fibers and introduction of bacteriostatic combinations; the invention can prepare the spinning fiber with strong integrity, continuous and excellent bacteriostatic effect, realizes the prevention and control of mould from multiple angles, and has the advantages of good mould-proof effect and long mould-proof duration period.
Description
Technical Field
The invention relates to the technical field of spinning fibers, in particular to a multiple mildew-proof composite textile fabric and a preparation method thereof.
Background
With the progress of the times and the change of the aesthetic consciousness and knowledge structure of consumers, various requirements of the consumers on the clothes are continuously changed. Due to the continuous enhancement of the environmental awareness of consumers, the garment fabric has higher requirements on the quality of the garment fabric, and the garment fabric not only needs to show the beauty of vision and touch, but also needs to connote various practical functions such as ultraviolet resistance, antibacterial deodorization, mildew resistance, radiation resistance and the like. Today, the fast development of the clothing industry, people's requirements on clothing are not only requirements on the workmanship and style of clothing, but also requirements on the quality of clothing, so that the requirements on the clothing fabric need to keep up with the development of the clothing situation, and the characteristics of the fabrics, such as functionality, comfort, environmental protection, health and the like, become more and more concerned topics. The existing mildew-proof fabric is usually prepared by directly adding a mildew preventive into a material to obtain mildew-proof performance, but the combination of the mildew preventive and the raw material is only simple physical mixing, the integrity of the material is poor, the problems that the environment is polluted by the migration of the mildew preventive, the mildew preventive is lost to cause the reduction of the mildew-proof performance and the like exist, and the mildew preventive is easy to release and directly contact with the skin to cause damage.
The invention discloses an antibacterial and mildewproof textile fabric and a preparation method thereof, and belongs to the patent number CN201410660124.2 and the patent name 'antibacterial and mildewproof textile fabric and a preparation method thereof'. The antibacterial and mildew-proof textile fabric comprises, by mass, 60-80 parts of bamboo fibers, 10-30 parts of folium artemisiae argyi fibers, 10-20 parts of Chinese yew fibers, 5-10 parts of fluoroacrylate polymer emulsion, 5-10 parts of polypropylene glycol, 1-3 parts of nano chitin and 0.5-2 parts of a dispersing agent. The antibacterial and mildewproof textile fabric disclosed by the invention has no irritation to human skin, and has good effects of ventilation, antibiosis, mildewproof and health care.
The antibacterial mildew-proof agent has the disadvantages that the components are obtained by simple physical mixing, the concentration of the antibacterial groups in the material is reduced along with the time, and the antibacterial mildew-proof durability is poor.
Disclosure of Invention
The invention aims to overcome the problem of poor mildew resistance durability of the existing textile fabric and provides a multiple mildew-resistant composite textile fabric and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the multiple mildew-proof composite textile fabric is woven by modified viscose, and the modified viscose is prepared from the following raw materials in parts by weight: 70-80 parts of viscose stock solution, 10-20 parts of modified bamboo fiber, 5-10 parts of mildew-proof polymer and 1-3 parts of lauryl alcohol polyoxyethylene ether.
The invention takes the modified bamboo fiber as the base material, sodium carboxymethylcellulose as the viscose material, the mildewproof polymer with the modified base is added, and the dispersant lauryl polyoxyethylene ether is added during the spinning mixing, so that the spun fiber has better cohesive force, uniform dispersion among the components, good mechanical property, and strong and long-lasting antibacterial effect.
Preferably, the preparation process of the modified bamboo fiber comprises the following steps: (1) preparing bamboo fibers: soaking natural bamboo, fermenting and ultrasonically processing to obtain bamboo fiber with high flexibility and strength; (2) soaking modification: soaking the bamboo fiber prepared in the step (1) in a modifier chitosan-polypropylene alcohol-octamethacrylate polymer solution to prepare modified bamboo fiber for later use; the mass ratio of the bamboo fibers to the modifier is 1: 3-5.
The chitosan derivative can be used for pretreating bamboo fibers to obtain fiber products with antibacterial activity. The chitosan has a fine pore structure and capillary action, so that sweat in the fiber can be quickly diffused, bacteria are not easy to attach and breed, and the antibacterial effect is enhanced; the chitosan has no stimulation and high safety to the skin and has better environmental protection effect. For the chitosan-polypropylene alcohol-octa methacrylate mildew-proof polymer, chitosan cellulose is a natural high molecular polymer, and chitosan has good biocompatibility and degradability and wide sourcewith-NH2and-OH group, the polypropylene alcohol is also a water-soluble polymer, has-OH group, the two polymers can be crosslinked by aldehydes, thereby forming crosslinked polymer, but the polymer prepared by taking chitosan alone as raw material has the problems of large brittleness, low strength and the like, and the polypropylene alcohol-chitosan solution prepared by adding the polypropylene alcohol into the chitosan solution can improve the swelling performance of the chitosan. The unique chain structure of chitosan in the solution can permeate into the cell wall of bamboo fiber, and an interpenetrating polymer network structure can be formed in the bamboo fiber. The bamboo fiber contains a large amount of hydroxyl, and can form intermolecular hydrogen bonds with amino and hydroxyl in the cross-linked polymer and react to form chemical bonds, so that interaction is generated, meanwhile, the polymer can block part of pores on the bamboo fiber, the effect of improving the dimensional stability of the bamboo fiber is achieved, and octamethacrylate is introduced into the polymer to improve the oleophylic property of the polymer, reduce the hydrophilicity of the polymer and inhibit the growth conditions of mold.
Preferably, the preparation method of the chitosan-polyallyl alcohol-octamethacrylate polymer comprises the following steps: dissolving chitosan cellulose in 10-15% acetic acid solution by mass, adding polypropylene glycol, stirring and dissolving in a constant-temperature water bath at 60-70 ℃, cooling, adding 1, 5-glutaraldehyde solution, fully stirring, reacting for 1-1.5h at constant temperature of 45-55 ℃, adding octamethacrylate into the solution, slowly heating to 100-105 ℃, and reacting for 1.5-2 h.
Preferably, the mass ratio of the chitosan cellulose to the polypropylene glycol to the 1, 5-glutaraldehyde to the octamethacrylate is 1: 6-8: 0.15-0.3: 2-3.
Preferably, the preparation steps of the mildew-proof polymer are as follows:
A. free radical polymerization: adding glycidyl methacrylate and hydroxyethyl methacrylate into chloroform, introducing nitrogen for 10-20min, adding azoisobutyronitrile, carrying out reflux stirring reaction on a reaction system under the protection of water bath nitrogen at 60-70 ℃ for 6-8h, and carrying out vacuum drying on the obtained product at 30-35 ℃ for 22-24 h; finally, washing the dried product with ethanol in a Soxhlet extractor for 8-9h, and drying to obtain a polymerization product;
B. ring opening reaction: adding the polymerization product into 0.1-0.12moL/L dilute nitric acid, and refluxing and stirring in a water bath at 40-45 ℃ for reaction for 4-5 h; then washing and filtering the reaction product by using distilled water, and then drying the reaction product in vacuum at the temperature of between 30 and 35 ℃ to obtain a ring-opening product; the mass ratio of the polymerization product to the dilute nitric acid is 1: 0.8-1.2;
C. and (3) performing a chloric acylation reaction: swelling the ring-opening product in dimethylformamide, adding anhydrous pyridine, dropwise adding chloroacetyl chloride in an ice salt bath under the protection of nitrogen, after dropwise adding, magnetically stirring at room temperature for reaction for 10-12h, and after complete reaction, washing with distilled water to neutrality to obtain a chloro-acylation product;
D. quaternization reaction: swelling the chloroacylation product in dimethyl sulfoxide, dropwise adding triethylamine, after dropwise adding, magnetically stirring for 8-10h at 48-52 ℃ in a water bath, and after complete reaction, washing with distilled water to obtain a final product.
The mildew-proof additive provided by the invention takes glycidyl methacrylate and hydroxyethyl methacrylate as raw materials, and the cationic quaternary ammonium salt polymer material with a good antibacterial function is prepared through modification research. The cationic quaternary ammonium salt polymer has the characteristics of high antibacterial spectrum, low toxicity, good solubility and wide pH range, and has strong antibacterial advantage compared with other antibacterial agents; compared with quaternary ammonium salt with low molecular weight, the cationic quaternary ammonium salt polymer has high charge density, and the cell membrane surface of bacteria or fungi has negative charge, so that the cationic quaternary ammonium salt polymer adsorbs more bacteria through electrostatic attraction, so that a large amount of cytoplasm components are lost, the normal physiological function of the cytoplasm components is damaged, and the bacteria die, and the polymer has stronger bacteriostatic effect.
Preferably, in the step A, the mass ratio of chloroform to glycidyl methacrylate to hydroxyethyl methacrylate to azoisobutyronitrile is 8-10: 5: 5-6: 0.3-0.5.
Preferably, in the step C, the mass ratio of the ring-opening product, dimethylformamide, anhydrous pyridine and chloroacetyl chloride is 1: 15-20: 0.5-0.8: 0.3-0.5.
Preferably, in the step D, the mass ratio of the chloracylation product to the dimethyl sulfoxide to the triethylamine is 1: 10-12: 0.4-0.8.
A preparation method of a multiple-mildew-proof composite textile fabric comprises the following steps:
I. preparing modified viscose fibers: adding viscose stock solution, modified bamboo fibers, a mildew-proof polymer and lauryl polyoxyethylene ether into a spinning assembly, uniformly mixing to obtain spinning solution, wherein the temperature of a spinning box is 30-60 ℃, the spinning solution is sprayed out from spinneret orifices of a spinneret plate of the spinning assembly to form trickle, and the trickle enters an acid coagulation bath at 15-40 ℃ to form nascent fibers; stretching, washing, dehydrating and drying the nascent fiber to obtain modified viscose fiber, and performing hydrophobic modification on the prepared modified viscose fiber;
II. Preparing a textile fabric: and (3) spinning the hydrophobic modified viscose to prepare the mildew-proof textile fabric.
The mildew-proof polymer, the modified components in the modified bamboo fibers and the bamboo fibers form stable chemical bonds, so that the spinning fibers have better integrity finally, and multiple optimization effects from preventing bacteria from breeding to inhibiting bacteria from growing are achieved.
Preferably, the hydrophobization modification process is: dipping the modified viscose fiber in a perfluoroalkyl silane solution dispersed by normal hexane for 1-2h, wherein the volume ratio of the perfluoroalkyl silane solution to the normal hexane is 1: 20-30.
Moisture and temperature are two major factors promoting the growth of mold, wherein the greatest influence is moisture, and the control method of the mold comprises the steps of ensuring the drying of the textile fabric as much as possible, and indirectly providing nutrition for the growth of the mold when stains are immersed into the spinning fibers. Therefore, the hydrophobic layer is coated on the surface of the spinning fiber, a chemical bond is formed between the hydrophobic layer and the spinning fiber component, the integration performance is good, a strong hydrophobic effect can be achieved, the water stains are prevented from invading the spinning fiber, the growth conditions of the mold are damaged, and the probability of mold breeding is reduced. The invention realizes multiple inhibition on mould from multiple angles, and has better mould-proof effect.
Therefore, the invention has the following beneficial effects:
(1) the invention provides a multiple mildew-proof composite textile fabric and a preparation method thereof, wherein a long-lasting bacteriostatic and mildew-proof effect is realized by introducing bacteriostatic functional groups, and multiple bacteriostatic effects are realized by bacteriostatic modification of natural bamboo fibers and introduction of bacteriostatic combinations;
(2) the invention makes special modification from the antibacterial property of the bamboo fiber modified component to the bactericidal property of the mildew-proof polymer, and from the increase of the antibacterial capability of the material to the introduction of the bactericidal polymer, prepares the spinning fiber with strong integrity, continuous and excellent antibacterial effect, realizes the prevention and control of the mildew from multiple angles, and has the advantages of good mildew-proof effect and long mildew-proof duration period;
(3) finally, the surface of the spinning fiber is subjected to waterproof modification, so that the spinning fiber has good water repellency, the fiber is not easy to mildew when the environment is humid, the antibacterial effect of the textile fabric is better promoted, the preparation method is simple, and the cost is saved.
Detailed Description
The invention is further described with reference to specific embodiments.
Example 1
1. Preparing a chitosan-polypropylene alcohol-octamethacrylate polymer: dissolving chitosan cellulose in an acetic acid solution with the mass fraction of 12%, adding polypropylene glycol, stirring and dissolving in a constant-temperature water bath at 65 ℃, cooling, adding a 1, 5-glutaraldehyde solution, fully stirring, reacting at the constant temperature of 50 ℃ for 1.2h, adding octamethacrylate into the solution, slowly heating to 102 ℃, and reacting for 1.8 h; the mass ratio of the chitosan cellulose to the polypropylene glycol to the 1, 5-glutaraldehyde to the octamethacrylate is 1: 7: 0.22: 2.5.
2. preparing modified bamboo fibers: (1) preparing bamboo fibers: soaking natural bamboo, fermenting and ultrasonically processing to obtain bamboo fiber with high flexibility and strength; (2) soaking modification: soaking the bamboo fiber prepared in the step (1) in a modifier chitosan-polypropylene alcohol-octamethacrylate polymer solution to prepare modified bamboo fiber for later use; the mass ratio of the bamboo fibers to the modifier is 1: 4.
3. preparation of a mildew-resistant polymer:
A. free radical polymerization: adding glycidyl methacrylate and hydroxyethyl methacrylate into chloroform, introducing nitrogen for 15min, adding azoisobutyronitrile, carrying out reflux stirring reaction on a reaction system under the protection of water bath nitrogen at 65 ℃ for 7h, and carrying out vacuum drying on the obtained product at 32 ℃ for 23 h; finally, washing the dried product with ethanol in a Soxhlet extractor for 8.5h, and drying to obtain a polymerization product; the mass ratio of chloroform to glycidyl methacrylate to hydroxyethyl methacrylate to azoisobutyronitrile is 9: 5: 5.5: 0.4;
B. ring opening reaction: adding the polymerization product into 0.11moL/L dilute nitric acid, and carrying out reflux stirring reaction in a water bath at 42 ℃ for 4.5 hours; then washing and filtering the reaction product by using distilled water, and then drying the reaction product in vacuum at the temperature of 32 ℃ to obtain a ring-opening product; the mass ratio of the polymerization product to the dilute nitric acid is 1: 1;
C. and (3) performing a chloric acylation reaction: swelling the ring-opening product in dimethylformamide, adding anhydrous pyridine, dropwise adding chloroacetyl chloride in an ice salt bath under the protection of nitrogen, after dropwise adding, magnetically stirring at room temperature for reaction for 11 hours, and after the reaction is completed, washing with distilled water to be neutral to obtain a chloro-acylation product; the mass ratio of the ring-opening product to the dimethylformamide to the anhydrous pyridine to the chloroacetyl chloride is 1: 18: 0.65: 0.4;
D. quaternization reaction: swelling a chloroacylation product in dimethyl sulfoxide, dropwise adding triethylamine, after dropwise adding, magnetically stirring for 9 hours at the temperature of 50 ℃ in a water bath, and after complete reaction, washing with distilled water to obtain a final product; the mass ratio of the chloro-acylation product to the dimethyl sulfoxide to the triethylamine is 1: 11: 0.6.
4. the preparation method of the multiple mildew-proof composite textile fabric comprises the following steps:
I. preparing modified viscose fibers: adding 75 parts of viscose stock solution, 15 parts of modified bamboo fiber, 8 parts of mildew-proof polymer and 2 parts of lauryl polyoxyethylene ether into a spinning assembly, uniformly mixing to obtain spinning solution, wherein the temperature of a spinning box is 45 ℃, the spinning solution is sprayed out from a spinneret orifice of a spinneret plate of the spinning assembly to form trickle, and the trickle enters an acid coagulation bath at the temperature of 25 ℃ to form nascent fiber; the nascent fiber is stretched, washed, dehydrated and dried to obtain modified viscose fiber;
II. Hydrophobic modification: soaking the modified viscose fiber in a perfluoroalkyl silane solution dispersed by n-hexane for 1.5h, wherein the volume ratio of the perfluoroalkyl silane solution to the n-hexane is 1: 25;
III, preparing a textile fabric: and (3) spinning the hydrophobic modified viscose to prepare the mildew-proof textile fabric.
Example 2
The difference from example 1 is that 1, chitosan-polyallyl alcohol-octamethacrylate polymer is prepared: dissolving chitosan cellulose in 10% acetic acid solution by mass, adding polypropylene glycol, stirring and dissolving in a constant-temperature water bath at 65 ℃, cooling, adding 1, 5-glutaraldehyde solution, fully stirring, reacting at 50 ℃ for 1h at constant temperature, adding octamethacrylate into the solution, slowly heating to 102 ℃, and reacting for 1.8 h; the mass ratio of the chitosan cellulose to the polypropylene glycol to the 1, 5-glutaraldehyde to the octamethacrylate is 1: 6: 0.3: 2.
2. preparing modified bamboo fibers: (1) preparing bamboo fibers: soaking natural bamboo, fermenting and ultrasonically processing to obtain bamboo fiber with high flexibility and strength; (2) soaking modification: soaking the bamboo fiber prepared in the step (1) in a modifier chitosan-polypropylene alcohol-octamethacrylate polymer solution to prepare modified bamboo fiber for later use; the mass ratio of the bamboo fibers to the modifier is 1: 3.
3. preparation of a mildew-resistant polymer:
A. free radical polymerization: adding glycidyl methacrylate and hydroxyethyl methacrylate into chloroform, introducing nitrogen for 10min, adding azoisobutyronitrile, carrying out reflux stirring reaction on a reaction system under the protection of water bath nitrogen at 65 ℃ for 7h, and carrying out vacuum drying on the obtained product at 32 ℃ for 23 h; finally, washing the dried product with ethanol in a Soxhlet extractor for 8.5h, and drying to obtain a polymerization product; the mass ratio of chloroform to glycidyl methacrylate to hydroxyethyl methacrylate to azoisobutyronitrile is 8: 5: 5: 0.5;
B. ring opening reaction: adding the polymerization product into 0.1moL/L dilute nitric acid, and carrying out reflux stirring reaction in a water bath at 42 ℃ for 4.5 hours; then washing the reaction product with distilled water, filtering, and then drying in vacuum at 30 ℃ to obtain a ring-opening product; the mass ratio of the polymerization product to the dilute nitric acid is 1: 0.8;
C. and (3) performing a chloric acylation reaction: swelling the ring-opening product in dimethylformamide, adding anhydrous pyridine, dropwise adding chloroacetyl chloride in an ice salt bath under the protection of nitrogen, after dropwise adding, magnetically stirring at room temperature for reaction for 11 hours, and after the reaction is completed, washing with distilled water to be neutral to obtain a chloro-acylation product; the mass ratio of the ring-opening product to the dimethylformamide to the anhydrous pyridine to the chloroacetyl chloride is 1: 15: 0.8: 0.3;
D. quaternization reaction: swelling a chloroacylation product in dimethyl sulfoxide, dropwise adding triethylamine, after dropwise adding, magnetically stirring for 9 hours at the temperature of 50 ℃ in a water bath, and after complete reaction, washing with distilled water to obtain a final product; the mass ratio of the chloro-acylation product to the dimethyl sulfoxide to the triethylamine is 1: 10: 0.8.
4. the preparation method of the multiple mildew-proof composite textile fabric comprises the following steps:
I. preparing modified viscose fibers: adding 70 parts of viscose stock solution, 20 parts of modified bamboo fiber, 5 parts of mildew-proof polymer and 3 parts of lauryl polyoxyethylene ether into a spinning assembly, uniformly mixing to obtain spinning solution, wherein the temperature of a spinning box is 45 ℃, the spinning solution is sprayed out from a spinneret orifice of a spinneret plate of the spinning assembly to form trickle, and the trickle enters an acid coagulation bath at the temperature of 25 ℃ to form nascent fiber; the nascent fiber is stretched, washed, dehydrated and dried to obtain modified viscose fiber;
II. Hydrophobic modification: soaking the modified viscose fiber in a perfluoroalkyl silane solution dispersed by n-hexane for 1.5h, wherein the volume ratio of the perfluoroalkyl silane solution to the n-hexane is 1: 20;
III, preparing a textile fabric: and (3) spinning the hydrophobic modified viscose to prepare the mildew-proof textile fabric.
Example 3
The difference from example 1 is that 1, chitosan-polyallyl alcohol-octamethacrylate polymer is prepared: dissolving chitosan cellulose in an acetic acid solution with the mass fraction of 15%, adding polypropylene glycol, stirring and dissolving in a constant-temperature water bath at 65 ℃, cooling, adding a 1, 5-glutaraldehyde solution, fully stirring, reacting at the constant temperature of 50 ℃ for 1.5h, adding octamethacrylate into the solution, slowly heating to 102 ℃, and reacting for 1.8 h; the mass ratio of the chitosan cellulose to the polypropylene glycol to the 1, 5-glutaraldehyde to the octamethacrylate is 1: 8: 0.15: 3.
2. preparing modified bamboo fibers: (1) preparing bamboo fibers: soaking natural bamboo, fermenting and ultrasonically processing to obtain bamboo fiber with high flexibility and strength; (2) soaking modification: soaking the bamboo fiber prepared in the step (1) in a modifier chitosan-polypropylene alcohol-octamethacrylate polymer solution to prepare modified bamboo fiber for later use; the mass ratio of the bamboo fibers to the modifier is 1: 5.
3. preparation of a mildew-resistant polymer:
A. free radical polymerization: adding glycidyl methacrylate and hydroxyethyl methacrylate into chloroform, introducing nitrogen for 20min, adding azoisobutyronitrile, carrying out reflux stirring reaction on a reaction system under the protection of water bath nitrogen at 65 ℃ for 7h, and carrying out vacuum drying on the obtained product at 32 ℃ for 23 h; finally, washing the dried product with ethanol in a Soxhlet extractor for 8.5h, and drying to obtain a polymerization product; the mass ratio of chloroform to glycidyl methacrylate to hydroxyethyl methacrylate to azoisobutyronitrile is 10: 5: 6: 0.3;
B. ring opening reaction: adding the polymerization product into 0.12moL/L dilute nitric acid, and carrying out reflux stirring reaction in a water bath at 42 ℃ for 4.5 hours; then washing the reaction product with distilled water, filtering, and then drying in vacuum at 35 ℃ to obtain a ring-opening product; the mass ratio of the polymerization product to the dilute nitric acid is 1: 1.2;
C. and (3) performing a chloric acylation reaction: swelling the ring-opening product in dimethylformamide, adding anhydrous pyridine, dropwise adding chloroacetyl chloride in an ice salt bath under the protection of nitrogen, after dropwise adding, magnetically stirring at room temperature for reaction for 11 hours, and after the reaction is completed, washing with distilled water to be neutral to obtain a chloro-acylation product; the mass ratio of the ring-opening product to the dimethylformamide to the anhydrous pyridine to the chloroacetyl chloride is 1: 15: 0.8: 0.3;
D. quaternization reaction: swelling a chloroacylation product in dimethyl sulfoxide, dropwise adding triethylamine, after dropwise adding, magnetically stirring for 9 hours at the temperature of 50 ℃ in a water bath, and after complete reaction, washing with distilled water to obtain a final product; the mass ratio of the chloro-acylation product to the dimethyl sulfoxide to the triethylamine is 1: 10: 0.8.
4. the preparation method of the multiple mildew-proof composite textile fabric comprises the following steps:
I. preparing modified viscose fibers: adding 70 parts of viscose stock solution, 20 parts of modified bamboo fiber, 10 parts of mildew-proof polymer and 1 part of lauryl polyoxyethylene ether into a spinning assembly, uniformly mixing to obtain spinning solution, wherein the temperature of a spinning box is 45 ℃, the spinning solution is sprayed out from a spinneret orifice of a spinneret plate of the spinning assembly to form trickle, and the trickle enters an acid coagulation bath at 25 ℃ to form nascent fiber; the nascent fiber is stretched, washed, dehydrated and dried to obtain modified viscose fiber;
II. Hydrophobic modification: soaking the modified viscose fiber in a perfluoroalkyl silane solution dispersed by n-hexane for 1.5h, wherein the volume ratio of the perfluoroalkyl silane solution to the n-hexane is 1: 30, of a nitrogen-containing gas;
III, preparing a textile fabric: and (3) spinning the hydrophobic modified viscose to prepare the mildew-proof textile fabric.
Example 4
The difference from example 1 is that 1, chitosan-polyallyl alcohol-octamethacrylate polymer is prepared: dissolving chitosan cellulose in an acetic acid solution with the mass fraction of 14%, adding polypropylene glycol, stirring and dissolving in a constant-temperature water bath at 65 ℃, cooling, adding a 1, 5-glutaraldehyde solution, fully stirring, reacting at the constant temperature of 50 ℃ for 1.5h, adding octamethacrylate into the solution, slowly heating to 102 ℃, and reacting for 1.8 h; the mass ratio of the chitosan cellulose to the polypropylene glycol to the 1, 5-glutaraldehyde to the octamethacrylate is 1: 7.5: 0.25: 2.7.
2. preparing modified bamboo fibers: (1) preparing bamboo fibers: soaking natural bamboo, fermenting and ultrasonically processing to obtain bamboo fiber with high flexibility and strength; (2) soaking modification: soaking the bamboo fiber prepared in the step (1) in a modifier chitosan-polypropylene alcohol-octamethacrylate polymer solution to prepare modified bamboo fiber for later use; the mass ratio of the bamboo fibers to the modifier is 1: 4.5.
3. preparation of a mildew-resistant polymer:
A. free radical polymerization: adding glycidyl methacrylate and hydroxyethyl methacrylate into chloroform, introducing nitrogen for 18min, adding azoisobutyronitrile, carrying out reflux stirring reaction on a reaction system under the protection of water bath nitrogen at 65 ℃ for 7h, and carrying out vacuum drying on the obtained product at 32 ℃ for 23 h; finally, washing the dried product with ethanol in a Soxhlet extractor for 8.5h, and drying to obtain a polymerization product; the mass ratio of chloroform to glycidyl methacrylate to hydroxyethyl methacrylate to azoisobutyronitrile is 9.5: 5: 5.8: 0.4;
B. ring opening reaction: adding the polymerization product into 0.12moL/L dilute nitric acid, and carrying out reflux stirring reaction in a water bath at 42 ℃ for 4.5 hours; then washing the reaction product with distilled water, filtering, and then drying in vacuum at 34 ℃ to obtain a ring-opening product; the mass ratio of the polymerization product to the dilute nitric acid is 1: 1.1;
C. and (3) performing a chloric acylation reaction: swelling the ring-opening product in dimethylformamide, adding anhydrous pyridine, dropwise adding chloroacetyl chloride in an ice salt bath under the protection of nitrogen, after dropwise adding, magnetically stirring at room temperature for reaction for 11 hours, and after the reaction is completed, washing with distilled water to be neutral to obtain a chloro-acylation product; the mass ratio of the ring-opening product to the dimethylformamide to the anhydrous pyridine to the chloroacetyl chloride is 1: 18: 0.6: 0.3;
D. quaternization reaction: swelling a chloroacylation product in dimethyl sulfoxide, dropwise adding triethylamine, after dropwise adding, magnetically stirring for 9 hours at the temperature of 50 ℃ in a water bath, and after complete reaction, washing with distilled water to obtain a final product; the mass ratio of the chloro-acylation product to the dimethyl sulfoxide to the triethylamine is 1: 10.5: 0.7.
4. the preparation method of the multiple mildew-proof composite textile fabric comprises the following steps:
I. preparing modified viscose fibers: adding 78 parts of viscose stock solution, 18 parts of modified bamboo fiber, 6 parts of mildew-proof polymer and 2.5 parts of lauryl polyoxyethylene ether into a spinning assembly, uniformly mixing to obtain spinning solution, wherein the temperature of a spinning box is 45 ℃, the spinning solution is sprayed out from a spinneret orifice of a spinneret plate of the spinning assembly to form trickle, and the trickle enters an acid coagulation bath at 25 ℃ to form nascent fiber; the nascent fiber is stretched, washed, dehydrated and dried to obtain modified viscose fiber;
II. Hydrophobic modification: soaking the modified viscose fiber in a perfluoroalkyl silane solution dispersed by n-hexane for 1.5h, wherein the volume ratio of the perfluoroalkyl silane solution to the n-hexane is 1: 28;
III, preparing a textile fabric: and (3) spinning the hydrophobic modified viscose to prepare the mildew-proof textile fabric.
Comparative example 1 (different from example 1 in that the bamboo fiber was not modified.)
1. Preparation of a mildew-resistant polymer:
A. free radical polymerization: adding glycidyl methacrylate and hydroxyethyl methacrylate into chloroform, introducing nitrogen for 15min, adding azoisobutyronitrile, carrying out reflux stirring reaction on a reaction system under the protection of water bath nitrogen at 65 ℃ for 7h, and carrying out vacuum drying on the obtained product at 32 ℃ for 23 h; finally, washing the dried product with ethanol in a Soxhlet extractor for 8.5h, and drying to obtain a polymerization product; the mass ratio of chloroform to glycidyl methacrylate to hydroxyethyl methacrylate to azoisobutyronitrile is 9: 5: 5.5: 0.4;
B. ring opening reaction: adding the polymerization product into 0.11moL/L dilute nitric acid, and carrying out reflux stirring reaction in a water bath at 42 ℃ for 4.5 hours; then washing and filtering the reaction product by using distilled water, and then drying the reaction product in vacuum at the temperature of 32 ℃ to obtain a ring-opening product; the mass ratio of the polymerization product to the dilute nitric acid is 1: 1;
C. and (3) performing a chloric acylation reaction: swelling the ring-opening product in dimethylformamide, adding anhydrous pyridine, dropwise adding chloroacetyl chloride in an ice salt bath under the protection of nitrogen, after dropwise adding, magnetically stirring at room temperature for reaction for 11 hours, and after the reaction is completed, washing with distilled water to be neutral to obtain a chloro-acylation product; the mass ratio of the ring-opening product to the dimethylformamide to the anhydrous pyridine to the chloroacetyl chloride is 1: 18: 0.65: 0.4;
D. quaternization reaction: swelling a chloroacylation product in dimethyl sulfoxide, dropwise adding triethylamine, after dropwise adding, magnetically stirring for 9 hours at the temperature of 50 ℃ in a water bath, and after complete reaction, washing with distilled water to obtain a final product; the mass ratio of the chloro-acylation product to the dimethyl sulfoxide to the triethylamine is 1: 11: 0.6.
2. the preparation method of the multiple mildew-proof composite textile fabric comprises the following steps:
I. preparing modified viscose fibers: adding 75 parts of viscose stock solution, 8 parts of mildew-proof polymer and 2 parts of lauryl polyoxyethylene ether into a spinning assembly, uniformly mixing to obtain spinning solution, wherein the temperature of a spinning box is 45 ℃, and the spinning solution is sprayed out from spinneret holes of a spinneret plate of the spinning assembly to form trickle and enters an acid coagulation bath at 25 ℃ to form nascent fibers; the nascent fiber is stretched, washed, dehydrated and dried to obtain modified viscose fiber;
II. Hydrophobic modification: soaking the modified viscose fiber in a perfluoroalkyl silane solution dispersed by n-hexane for 1.5h, wherein the volume ratio of the perfluoroalkyl silane solution to the n-hexane is 1: 25;
III, preparing a textile fabric: and (3) spinning the hydrophobic modified viscose to prepare the mildew-proof textile fabric.
Comparative example 2 (different from example 1 in that no mildewproofing polymer was added.)
The difference from the embodiment 1 is that,
1. preparing a chitosan-polypropylene alcohol-octamethacrylate polymer: dissolving chitosan cellulose in an acetic acid solution with the mass fraction of 12%, adding polypropylene glycol, stirring and dissolving in a constant-temperature water bath at 65 ℃, cooling, adding a 1, 5-glutaraldehyde solution, fully stirring, reacting at the constant temperature of 50 ℃ for 1.2h, adding octamethacrylate into the solution, slowly heating to 102 ℃, and reacting for 1.8 h; the mass ratio of the chitosan cellulose to the polypropylene glycol to the 1, 5-glutaraldehyde to the octamethacrylate is 1: 7: 0.22: 2.5.
2. preparing modified bamboo fibers: (1) preparing bamboo fibers: soaking natural bamboo, fermenting and ultrasonically processing to obtain bamboo fiber with high flexibility and strength; (2) soaking modification: soaking the bamboo fiber prepared in the step (1) in a modifier chitosan-polypropylene alcohol-octamethacrylate polymer solution to prepare modified bamboo fiber for later use; the mass ratio of the bamboo fibers to the modifier is 1: 4.
3. the preparation method of the mildew-proof composite textile fabric comprises the following steps:
I. preparing modified viscose fibers: adding 75 parts of viscose stock solution, 15 parts of modified bamboo fiber and 2 parts of lauryl polyoxyethylene ether into a spinning assembly, uniformly mixing to obtain spinning solution, wherein the temperature of a spinning box is 45 ℃, the spinning solution is sprayed out from spinneret holes of a spinneret plate of the spinning assembly to form trickle, and the trickle enters an acid coagulation bath at 25 ℃ to form nascent fiber; the nascent fiber is stretched, washed, dehydrated and dried to obtain modified viscose fiber;
II. Hydrophobic modification: soaking the modified viscose fiber in a perfluoroalkyl silane solution dispersed by n-hexane for 1.5h, wherein the volume ratio of the perfluoroalkyl silane solution to the n-hexane is 1: 25;
III, preparing a textile fabric: and (3) spinning the hydrophobic modified viscose to prepare the mildew-proof textile fabric.
Comparative example 3 (different from example 1 in that the mildewproofing polymer was not quaternized.)
The difference from example 1 is that 1, chitosan-polyallyl alcohol-octamethacrylate polymer is prepared: dissolving chitosan cellulose in an acetic acid solution with the mass fraction of 12%, adding polypropylene glycol, stirring and dissolving in a constant-temperature water bath at 65 ℃, cooling, adding a 1, 5-glutaraldehyde solution, fully stirring, reacting at the constant temperature of 50 ℃ for 1.2h, adding octamethacrylate into the solution, slowly heating to 102 ℃, and reacting for 1.8 h; the mass ratio of the chitosan cellulose to the polypropylene glycol to the 1, 5-glutaraldehyde to the octamethacrylate is 1: 7: 0.22: 2.5.
2. preparing modified bamboo fibers: (1) preparing bamboo fibers: soaking natural bamboo, fermenting and ultrasonically processing to obtain bamboo fiber with high flexibility and strength; (2) soaking modification: soaking the bamboo fiber prepared in the step (1) in a modifier chitosan-polypropylene alcohol-octamethacrylate polymer solution to prepare modified bamboo fiber for later use; the mass ratio of the bamboo fibers to the modifier is 1: 4.
3. preparation of a mildew-resistant polymer:
A. free radical polymerization: adding glycidyl methacrylate and hydroxyethyl methacrylate into chloroform, introducing nitrogen for 15min, adding azoisobutyronitrile, carrying out reflux stirring reaction on a reaction system under the protection of water bath nitrogen at 65 ℃ for 7h, and carrying out vacuum drying on the obtained product at 32 ℃ for 23 h; finally, washing the dried product with ethanol in a Soxhlet extractor for 8.5h, and drying to obtain a polymerization product; the mass ratio of chloroform to glycidyl methacrylate to hydroxyethyl methacrylate to azoisobutyronitrile is 9: 5: 5.5: 0.4;
B. ring opening reaction: adding the polymerization product into 0.11moL/L dilute nitric acid, and carrying out reflux stirring reaction in a water bath at 42 ℃ for 4.5 hours; then washing and filtering the reaction product by using distilled water, and then drying the reaction product in vacuum at the temperature of 32 ℃ to obtain a ring-opening product; the mass ratio of the polymerization product to the dilute nitric acid is 1: 1;
C. and (3) performing a chloric acylation reaction: swelling the ring-opening product in dimethylformamide, adding anhydrous pyridine, dropwise adding chloroacetyl chloride in an ice salt bath under the protection of nitrogen, after dropwise adding, magnetically stirring at room temperature for reaction for 11 hours, and after the reaction is completed, washing with distilled water to be neutral to obtain a chloro-acylation product; the mass ratio of the ring-opening product to the dimethylformamide to the anhydrous pyridine to the chloroacetyl chloride is 1: 18: 0.65: 0.4.
4. the preparation method of the multiple mildew-proof composite textile fabric comprises the following steps:
I. preparing modified viscose fibers: adding 75 parts of viscose stock solution, 15 parts of modified bamboo fiber, 8 parts of mildew-proof polymer and 2 parts of lauryl polyoxyethylene ether into a spinning assembly, uniformly mixing to obtain spinning solution, wherein the temperature of a spinning box is 45 ℃, the spinning solution is sprayed out from a spinneret orifice of a spinneret plate of the spinning assembly to form trickle, and the trickle enters an acid coagulation bath at the temperature of 25 ℃ to form nascent fiber; the nascent fiber is stretched, washed, dehydrated and dried to obtain modified viscose fiber;
II. Hydrophobic modification: soaking the modified viscose fiber in a perfluoroalkyl silane solution dispersed by n-hexane for 1.5h, wherein the volume ratio of the perfluoroalkyl silane solution to the n-hexane is 1: 25;
III, preparing a textile fabric: and (3) spinning the hydrophobic modified viscose to prepare the mildew-proof textile fabric.
Comparative example 4 (different from example 1 in that the spun fiber was not water-repellent-modified.)
The difference from example 1 is that 1, chitosan-polyallyl alcohol-octamethacrylate polymer is prepared: dissolving chitosan cellulose in an acetic acid solution with the mass fraction of 12%, adding polypropylene glycol, stirring and dissolving in a constant-temperature water bath at 65 ℃, cooling, adding a 1, 5-glutaraldehyde solution, fully stirring, reacting at the constant temperature of 50 ℃ for 1.2h, adding octamethacrylate into the solution, slowly heating to 102 ℃, and reacting for 1.8 h; the mass ratio of the chitosan cellulose to the polypropylene glycol to the 1, 5-glutaraldehyde to the octamethacrylate is 1: 7: 0.22: 2.5.
2. preparing modified bamboo fibers: (1) preparing bamboo fibers: soaking natural bamboo, fermenting and ultrasonically processing to obtain bamboo fiber with high flexibility and strength; (2) soaking modification: soaking the bamboo fiber prepared in the step (1) in a modifier chitosan-polypropylene alcohol-octamethacrylate polymer solution to prepare modified bamboo fiber for later use; the mass ratio of the bamboo fibers to the modifier is 1: 4.
3. preparation of a mildew-resistant polymer:
A. free radical polymerization: adding glycidyl methacrylate and hydroxyethyl methacrylate into chloroform, introducing nitrogen for 15min, adding azoisobutyronitrile, carrying out reflux stirring reaction on a reaction system under the protection of water bath nitrogen at 65 ℃ for 7h, and carrying out vacuum drying on the obtained product at 32 ℃ for 23 h; finally, washing the dried product with ethanol in a Soxhlet extractor for 8.5h, and drying to obtain a polymerization product; the mass ratio of chloroform to glycidyl methacrylate to hydroxyethyl methacrylate to azoisobutyronitrile is 9: 5: 5.5: 0.4;
B. ring opening reaction: adding the polymerization product into 0.11moL/L dilute nitric acid, and carrying out reflux stirring reaction in a water bath at 42 ℃ for 4.5 hours; then washing and filtering the reaction product by using distilled water, and then drying the reaction product in vacuum at the temperature of 32 ℃ to obtain a ring-opening product; the mass ratio of the polymerization product to the dilute nitric acid is 1: 1;
C. and (3) performing a chloric acylation reaction: swelling the ring-opening product in dimethylformamide, adding anhydrous pyridine, dropwise adding chloroacetyl chloride in an ice salt bath under the protection of nitrogen, after dropwise adding, magnetically stirring at room temperature for reaction for 11 hours, and after the reaction is completed, washing with distilled water to be neutral to obtain a chloro-acylation product; the mass ratio of the ring-opening product to the dimethylformamide to the anhydrous pyridine to the chloroacetyl chloride is 1: 18: 0.65: 0.4;
D. quaternization reaction: swelling a chloroacylation product in dimethyl sulfoxide, dropwise adding triethylamine, after dropwise adding, magnetically stirring for 9 hours at the temperature of 50 ℃ in a water bath, and after complete reaction, washing with distilled water to obtain a final product; the mass ratio of the chloro-acylation product to the dimethyl sulfoxide to the triethylamine is 1: 11: 0.6.
4. the preparation method of the multiple mildew-proof composite textile fabric comprises the following steps:
I. preparing modified viscose fibers: adding 75 parts of viscose stock solution, 15 parts of modified bamboo fiber, 8 parts of mildew-proof polymer and 2 parts of lauryl polyoxyethylene ether into a spinning assembly, uniformly mixing to obtain spinning solution, wherein the temperature of a spinning box is 45 ℃, the spinning solution is sprayed out from a spinneret orifice of a spinneret plate of the spinning assembly to form trickle, and the trickle enters an acid coagulation bath at the temperature of 25 ℃ to form nascent fiber; the nascent fiber is stretched, washed, dehydrated and dried to obtain modified viscose fiber;
II. Preparing a textile fabric: and (3) spinning the modified viscose to prepare the mildew-proof textile fabric.
Comparative example 5 (different from example 1 in that hydroxyethyl methacrylate, which is a polymerization component in the mildewproof polymer, is replaced with vinyl acetate.)
The difference from example 1 is that 1, chitosan-polyallyl alcohol-octamethacrylate polymer is prepared: dissolving chitosan cellulose in an acetic acid solution with the mass fraction of 12%, adding polypropylene glycol, stirring and dissolving in a constant-temperature water bath at 65 ℃, cooling, adding a 1, 5-glutaraldehyde solution, fully stirring, reacting at the constant temperature of 50 ℃ for 1.2h, adding octamethacrylate into the solution, slowly heating to 102 ℃, and reacting for 1.8 h; the mass ratio of the chitosan cellulose to the polypropylene glycol to the 1, 5-glutaraldehyde to the octamethacrylate is 1: 7: 0.22: 2.5.
2. preparing modified bamboo fibers: (1) preparing bamboo fibers: soaking natural bamboo, fermenting and ultrasonically processing to obtain bamboo fiber with high flexibility and strength; (2) soaking modification: soaking the bamboo fiber prepared in the step (1) in a modifier chitosan-polypropylene alcohol-octamethacrylate polymer solution to prepare modified bamboo fiber for later use; the mass ratio of the bamboo fibers to the modifier is 1: 4.
3. preparation of a mildew-resistant polymer:
A. free radical polymerization: adding glycidyl methacrylate and vinyl acetate into chloroform, introducing nitrogen for 15min, adding azoisobutyronitrile, carrying out reflux stirring reaction on a reaction system under the protection of water bath nitrogen at 65 ℃ for 7h, and carrying out vacuum drying on the obtained product at 32 ℃ for 23 h; finally, washing the dried product with ethanol in a Soxhlet extractor for 8.5h, and drying to obtain a polymerization product; the mass ratio of chloroform to glycidyl methacrylate to vinyl acetate to azoisobutyronitrile is 9: 5: 5.5: 0.4;
B. ring opening reaction: adding the polymerization product into 0.11moL/L dilute nitric acid, and carrying out reflux stirring reaction in a water bath at 42 ℃ for 4.5 hours; then washing and filtering the reaction product by using distilled water, and then drying the reaction product in vacuum at the temperature of 32 ℃ to obtain a ring-opening product; the mass ratio of the polymerization product to the dilute nitric acid is 1: 1;
C. and (3) performing a chloric acylation reaction: swelling the ring-opening product in dimethylformamide, adding anhydrous pyridine, dropwise adding chloroacetyl chloride in an ice salt bath under the protection of nitrogen, after dropwise adding, magnetically stirring at room temperature for reaction for 11 hours, and after the reaction is completed, washing with distilled water to be neutral to obtain a chloro-acylation product; the mass ratio of the ring-opening product to the dimethylformamide to the anhydrous pyridine to the chloroacetyl chloride is 1: 18: 0.65: 0.4;
D. quaternization reaction: swelling a chloroacylation product in dimethyl sulfoxide, dropwise adding triethylamine, after dropwise adding, magnetically stirring for 9 hours at the temperature of 50 ℃ in a water bath, and after complete reaction, washing with distilled water to obtain a final product; the mass ratio of the chloro-acylation product to the dimethyl sulfoxide to the triethylamine is 1: 11: 0.6.
4. the preparation method of the multiple mildew-proof composite textile fabric comprises the following steps:
I. preparing modified viscose fibers: adding 75 parts of viscose stock solution, 15 parts of modified bamboo fiber, 8 parts of mildew-proof polymer and 2 parts of lauryl polyoxyethylene ether into a spinning assembly, uniformly mixing to obtain spinning solution, wherein the temperature of a spinning box is 45 ℃, the spinning solution is sprayed out from a spinneret orifice of a spinneret plate of the spinning assembly to form trickle, and the trickle enters an acid coagulation bath at the temperature of 25 ℃ to form nascent fiber; the nascent fiber is stretched, washed, dehydrated and dried to obtain modified viscose fiber;
II. Hydrophobic modification: soaking the modified viscose fiber in a perfluoroalkyl silane solution dispersed by n-hexane for 1.5h, wherein the volume ratio of the perfluoroalkyl silane solution to the n-hexane is 1: 25;
III, preparing a textile fabric: and (3) spinning the hydrophobic modified viscose to prepare the mildew-proof textile fabric.
The physical property indexes of the water-repellent antifouling low-melting-point composite fibers prepared in examples 1 to 4 and comparative examples 1 to 5 are shown in Table 1.
TABLE 1 physical index of mildew-proof composite spinning fabric
And (4) conclusion: from examples 1 to 4, it can be seen that the fiber textile fabric prepared from the components and the content range of the components has good antibacterial and mildewproof performance, good antibacterial and mildewproof performance and strong antibacterial and mildewproof continuity.
Comparative example 1 is different from example 1 in that the bamboo fiber is not modified; the bamboo fiber is modified, so that the antibacterial and mildewproof performance of the final spinning fabric can be improved, the coupling force between the bamboo fiber and other components is enhanced, and the durability of the antibacterial and mildewproof capability of the spinning fiber is improved.
Comparative example 2 differs from example 1 in that no anti-mildew polymer was added; the mildew-proof polymer is not added, so that an antibacterial functional group cannot be introduced, the damage effect of mildew can be reduced, and the rapid volatilization effect of the chitosan porous structure in the chitosan polymer on the water inside the spinning fiber is only used for bacteriostasis, so that the bacteriostasis effect is finally deteriorated.
Comparative example 3 differs from example 1 in that the mildewproofing polymer is not quaternized; the damage capability of the mildew-proof polymer to the mildew is reduced, so that the antibacterial and mildew-proof effects are reduced.
Comparative example 4 differs from example 1 in that the spun fiber was not subjected to water-repellency modification; the spinning fibers can easily absorb surrounding water and stains, provide a large growth space for breeding of mold, easily promote the mold generation of the textile fabric, and have poor antibacterial and mildewproof continuous capability.
Comparative example 5 differs from example 1 in that the polymerization component hydroxyethyl methacrylate in the mold-resistant polymer is replaced by vinyl acetate; the active groups and the molecular chain length on the vinyl acetate are lower than those of hydroxyethyl methacrylate, so that the crosslinking capability and the stability of the formed polymer are much lower, and the antibacterial and mildewproof persistence of the finally prepared spinning fiber is poor.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified. The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. The multiple mildew-proof composite textile fabric is characterized in that the textile fabric is woven by modified viscose, and the modified viscose is prepared from the following raw materials in parts by weight: 70-80 parts of viscose stock solution, 10-20 parts of modified bamboo fiber, 5-10 parts of mildew-proof polymer and 1-3 parts of lauryl alcohol polyoxyethylene ether.
2. The multiple mildew-proof composite textile fabric according to claim 1, wherein the modified bamboo fiber is prepared by the following steps: (1) preparing bamboo fibers: soaking natural bamboo, fermenting and ultrasonically processing to obtain bamboo fiber with high flexibility and strength; (2) soaking modification: soaking the bamboo fiber prepared in the step (1) in a modifier chitosan-polypropylene alcohol-octamethacrylate polymer solution to prepare modified bamboo fiber for later use; the mass ratio of the bamboo fibers to the modifier is 1: 3-5.
3. The multiple mold-proof composite textile fabric according to claim 2, wherein the preparation step of the chitosan-polyallyl alcohol-octamethacrylate polymer comprises: dissolving chitosan cellulose in 10-15% acetic acid solution by mass, adding polypropylene glycol, stirring and dissolving in a constant-temperature water bath at 60-70 ℃, cooling, adding 1, 5-glutaraldehyde solution, fully stirring, reacting for 1-1.5h at constant temperature of 45-55 ℃, adding octamethacrylate into the solution, slowly heating to 100-105 ℃, and reacting for 1.5-2 h.
4. The multiple mildew-proof composite textile fabric according to claim 3, wherein the mass ratio of the chitosan cellulose, the polypropylene glycol, the 1, 5-glutaraldehyde and the octamethacrylate is 1: 6-8: 0.15-0.3: 2-3.
5. The multiple mildew-resistant composite textile fabric according to claim 1, wherein the mildew-resistant polymer is prepared by the following steps:
A. free radical polymerization: adding glycidyl methacrylate and hydroxyethyl methacrylate into chloroform, introducing nitrogen for 10-20min, adding azoisobutyronitrile, carrying out reflux stirring reaction on a reaction system under the protection of water bath nitrogen at 60-70 ℃ for 6-8h, and carrying out vacuum drying on the obtained product at 30-35 ℃ for 22-24 h; finally, washing the dried product with ethanol in a Soxhlet extractor for 8-9h, and drying to obtain a polymerization product;
B. ring opening reaction: adding the polymerization product into 0.1-0.12moL/L dilute nitric acid, and refluxing and stirring in a water bath at 40-45 ℃ for reaction for 4-5 h; then washing and filtering the reaction product by using distilled water, and then drying the reaction product in vacuum at the temperature of between 30 and 35 ℃ to obtain a ring-opening product; the mass ratio of the polymerization product to the dilute nitric acid is 1: 0.8-1.2;
C. and (3) performing a chloric acylation reaction: swelling the ring-opening product in dimethylformamide, adding anhydrous pyridine, dropwise adding chloroacetyl chloride in an ice salt bath under the protection of nitrogen, after dropwise adding, magnetically stirring at room temperature for reaction for 10-12h, and after complete reaction, washing with distilled water to neutrality to obtain a chloro-acylation product;
D. quaternization reaction: swelling the chloroacylation product in dimethyl sulfoxide, dropwise adding triethylamine, after dropwise adding, magnetically stirring for 8-10h at 48-52 ℃ in a water bath, and after complete reaction, washing with distilled water to obtain a final product.
6. The multiple mildew-proof composite textile fabric according to claim 5, wherein in the step A, the mass ratio of chloroform to glycidyl methacrylate to hydroxyethyl methacrylate to azoisobutyronitrile is 8-10: 5: 5-6: 0.3-0.5.
7. The multiple mildew-proof composite textile fabric according to claim 5, wherein in the step C, the mass ratio of the ring-opening product to the dimethylformamide to the anhydrous pyridine to the chloroacetyl chloride is 1: 15-20: 0.5-0.8: 0.3-0.5.
8. The multiple mildew-proof composite textile fabric according to claim 5, wherein in the step D, the mass ratio of the chloracylation product to the dimethyl sulfoxide to the triethylamine is 1: 10-12: 0.4-0.8.
9. A method for preparing the multiple mildew-resistant composite textile fabric according to any one of claims 1 to 8, comprising the following steps:
I. preparing modified viscose fibers: adding viscose stock solution, modified bamboo fibers, a mildew-proof polymer and lauryl polyoxyethylene ether into a spinning assembly, uniformly mixing to obtain spinning solution, wherein the temperature of a spinning box is 30-60 ℃, the spinning solution is sprayed out from spinneret orifices of a spinneret plate of the spinning assembly to form trickle, and the trickle enters an acid coagulation bath at 15-40 ℃ to form nascent fibers; stretching, washing, dehydrating and drying the nascent fiber to obtain modified viscose fiber, and performing hydrophobic modification on the prepared modified viscose fiber;
II. Preparing a textile fabric: and (3) spinning the hydrophobic modified viscose to prepare the mildew-proof textile fabric.
10. The method for preparing the multiple mildewproof composite textile fabric according to claim 9, wherein the hydrophobization modification process comprises the following steps: dipping the modified viscose fiber in a perfluoroalkyl silane solution dispersed by normal hexane for 1-2h, wherein the volume ratio of the perfluoroalkyl silane solution to the normal hexane is 1: 20-30.
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| EL-REFAIE KENAWY ET AL.: "Biologically active polymers. V. Synthesis and antimicrobial activity of modified poly(glycidyl methacrylate-co-2-hydroxyethyl methacrylate) derivatives with quaternary ammonium and phosphonium salts", 《JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY》 * |
| 杨秀树 等: "交联壳聚糖/聚乙烯醇的制备及其在竹材中的构建", 《林业工程学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112442771A (en) * | 2020-11-13 | 2021-03-05 | 浙江羊绒世家服饰有限公司 | Water-soluble fiber and high count cashmere yarn spinning process |
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Application publication date: 20200922 |