CN113136633B - A kind of long-acting antibacterial flame retardant double-effect lyocell fiber and preparation method thereof - Google Patents
A kind of long-acting antibacterial flame retardant double-effect lyocell fiber and preparation method thereof Download PDFInfo
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- 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
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Abstract
本发明属于纤维材料技术领域，公开了一种长效抑菌阻燃双效莱赛尔纤维及其制备方法。首先将莱赛尔纤维原料经Provetex cp阻燃改性，然后溶解于NMMO水溶液中，加入银盐水溶液搅拌混合均匀，得到纺丝溶液；往凝固浴溶液中加入碱调节pH值为碱性，得到反应性凝固浴；将纺丝溶液经纺丝后进入反应性凝固浴中凝固成形，得到长效抑菌阻燃双效莱赛尔纤维。本发明通过阻燃剂进行共价偶联改性，赋予纤维材料阻燃功效；且在莱赛尔纤维凝固成形的过程中原位反应引入氧化银抗菌剂，抗菌剂分散均匀、与纤维基体附着力强，所得抑菌纤维抗菌效果持久、耐水洗。本发明的制备方法简单、易工业化、成本较低。具有极好的商业应用前景。
The invention belongs to the technical field of fiber materials, and discloses a long-acting antibacterial and flame-retardant double-effect lyocell fiber and a preparation method thereof. First, the lyocell fiber raw material was modified by Provetex cp flame retardant, and then dissolved in NMMO aqueous solution, and the silver salt aqueous solution was added to stir and mix uniformly to obtain a spinning solution. Reactive coagulation bath; the spinning solution is spun into a reactive coagulation bath to coagulate and form to obtain a long-acting, bacteriostatic and flame-retardant double-effect lyocell fiber. In the present invention, the flame retardant is modified by covalent coupling to endow the fiber material with flame retardant effect; and the silver oxide antibacterial agent is introduced into the in-situ reaction during the solidification and forming process of the lyocell fiber, and the antibacterial agent is uniformly dispersed and has good adhesion to the fiber matrix. Strong, the obtained antibacterial fiber has a lasting antibacterial effect and is washable. The preparation method of the invention is simple, easy to industrialize and low in cost. It has excellent commercial application prospects.
Description
Technical Field
The invention belongs to the technical field of fiber materials, and particularly relates to a long-acting antibacterial flame-retardant double-effect lyocell fiber and a preparation method thereof.
Background
Lyocell fiber is commonly called as "velvet", is prepared from natural plant fiber as a raw material, is appeared in the middle of the 90 s of the 20 th century, and is known as the most valuable product in the history of artificial fiber for nearly half the century. The lyocell fiber has various excellent performances of natural fiber and synthetic fiber, lyocell is green fiber, raw materials of lyocell are inexhaustible cellulose in nature, a production process has no chemical reaction, and used solvents are nontoxic. The lyocell fiber has the warmth retention property of wool, does not generate static electricity and is anti-allergic in the wearing aspect, and simultaneously has the softness of cotton and the high strength and wear resistance of terylene. Has the luxury feeling of wool fabric and the draping feeling of modal in appearance, and is very suitable for making high-grade women's clothing with bright and beautiful surface. In washing, the anti-pilling and water shrinkage rate is low. In the hand feeling aspect, the silk fabric has the smooth touch feeling and soft feeling of silk. In the aspect of dyeing and printing, the color fixation is excellent and the color is not easy to fade.
The lyocell fiber is affected by the material (mainly cellulose) of the lyocell fiber, and the flame retardant effect is poor. Patent CN 112323159A discloses a flame-retardant lyocell fiber and a preparation method thereof, which adopts starch, phosphoric acid and urea as a synergistic intumescent flame retardant, wherein the starch is a char forming agent, the phosphoric acid is a dehydrating agent, and the urea is a foaming agent. The flame-retardant lyocell fiber does not have enough fuel and oxygen, so that the combustion is stopped, and the technical effect of improving the flame retardance of the fiber is achieved. Patent CN 109402756 a discloses a preparation method of flame retardant lyocell fiber, which is to uniformly mix cellulose and tris (2, 3-dibromopropyl) phosphate in NMMO aqueous solution to prepare lyocell fiber. The tris (2, 3-dibromopropyl) phosphate is an excellent flame retardant, and the prepared lyocell fiber also has excellent flame retardant property. Although the technical means can achieve a certain flame retardant effect, the fiber material is mainly prepared by a physical blending mode, and the strength of the fiber material is possibly adversely affected.
In addition, due to the natural green property of the lyocell fibers, the fabric prepared from the lyocell fibers also has good affinity for microorganisms such as bacteria, so that bacteria are easy to breed, and adverse effects are caused on human health. The antibacterial fiber is fiber with the functions of degerming and bacteriostasis. There are two general classes of antimicrobial fibers. One is fiber with antibacterial and bacteriostatic effects, such as hemp, herba Apocyni Veneti, chitin fiber, and metal fiber. The other is an antibacterial fiber prepared by adding an antibacterial agent to a fiber during spinning or modification of chemical fibers by means of a chelating technique, a nano technique, a powder adding technique and the like.
Patent CN 110962403 a discloses a lyocell fiber antibacterial blended fabric. The surface layer is made of a Lyocell fiber antibacterial fabric, the Lyocell fiber antibacterial fabric is formed by interweaving warps and wefts, the warps are blended yarns of Lyocell fibers and cotton fibers, and the wefts are blended yarns of mint fibers and cotton fibers. The lyocell fiber antibacterial fabric is prepared by adding an antibacterial finishing agent to treat for 30-40 minutes and then baking at 55 ℃ for 20-30 minutes.
Patent CN 108118425 a discloses an antibacterial warm-keeping self-cleaning shirt fabric. A nano titanium dioxide layer is closely adhered to the surface of the fabric base cloth; the fabric base cloth is formed by interweaving warp threads I, warp threads II, weft threads I and weft threads II in a staggered manner; the first warp is a yarn formed by interweaving and twisting wool fibers and lyocell fibers; the first weft is formed by interweaving and twisting bamboo charcoal fibers and combed cotton fibers; the second weft is a yarn formed by interweaving and twisting wool fibers and anti-pilling acrylic fibers; and the warp yarn II is an anti-pilling acrylic yarn. The surface layer of the fabric base cloth is adhered with the nano titanium dioxide layer through post-treatment to generate oxygen free radicals with strong oxidizing capability, so that the self-cleaning and antibacterial functions are realized.
Patent CN 109881478A discloses an antibacterial health-care functional cap decoration fabric. The cap decoration fabric is a plain weave and comprises warp yarns and weft yarns, wherein the warp yarns are cotton and Lyocell blended yarns, the blending ratio is 50:50, the yarn count is 14.6tex, the weft yarns are coconut charcoal and Lyocell blended yarns, the yarn count is 14.6tex, and the cap decoration fabric further comprises an antibacterial health-care material, and the antibacterial health-care material is arranged on the cap decoration fabric in a microcapsule mode. The coconut charcoal fiber is added into the fabric, and the hydroxypropyl chitosan and the procyanidine rich in grape seed extract are acted on the fabric, so that multiple effects of resisting bacteria, deodorizing, absorbing moisture, drying quickly, promoting blood circulation, resisting aging, resisting ultraviolet rays, releasing negative ions and the like are fully exerted. The microcapsule technology is adopted to effectively prolong the action time of the efficacy.
Although the prior art realizes the modification of the antibacterial function of the lyocell fiber to a certain degree, the prior art has the problems of not lasting antibacterial effect, not water washing resistance, complex preparation method, difficult industrialization and higher cost.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a preparation method of long-acting antibacterial flame-retardant double-effect lyocell fiber.
The invention also aims to provide the long-acting antibacterial flame-retardant double-effect lyocell fiber prepared by the method.
The purpose of the invention is realized by the following technical scheme:
a preparation method of long-acting antibacterial flame-retardant double-effect lyocell fibers comprises the following preparation steps:
(1) adding N-hydroxymethyl-3- (dimethoxyphosphono) propionamide (Provetex cp) and ethylene diamine tetraacetic acid into a reactor, stirring at 60-80 ℃ for reaction, vacuum dehydrating in the reaction process to promote the reaction, adding a Lyocell fiber raw material after the reaction is finished, and continuing the esterification reaction to obtain a flame-retardant modified Lyocell fiber raw material;
(2) preparation of spinning solution: dissolving a lyocell fiber raw material in an N-methylmorpholine-N-oxide (NMMO) aqueous solution, then adding a silver salt aqueous solution, and uniformly stirring and mixing to obtain a spinning solution;
(3) preparation of reactive coagulation bath: adding alkali into the coagulation bath solution to adjust the pH value to be alkaline, so as to obtain a reactive coagulation bath;
(4) and (3) spinning the spinning solution obtained in the step (2), and then allowing the spinning solution to enter the reactive coagulation bath obtained in the step (3) for coagulation forming to obtain the long-acting antibacterial flame-retardant double-effect lyocell fiber.
Further, the lyocell fiber raw material in the step (1) is a natural cellulose raw material such as hemp pulp, grass pulp, cotton pulp, wood pulp, bamboo pulp and the like.
The flame-retardant modified lyocell fiber raw material in the step (1) is obtained by performing flame-retardant modification on a lyocell fiber raw material through ethylenediamine tetraacetic acid-coupled N-hydroxymethyl-3- (dimethoxyphosphono) propionamide (Provetex cp), and a reaction scheme of the flame-retardant modified lyocell fiber raw material is shown in FIG. 1.
Further, the molar ratio of the Provetex cp to the ethylenediamine tetraacetic acid in the step (1) is 2:1, and the stirring reaction time is 3-4 h.
Further, the mass concentration of the NMMO aqueous solution in the step (2) is 90-99%.
Further, the silver salt aqueous solution in the step (2) is silver nitrate aqueous solution. The adding amount of the silver nitrate water solution is 0.2-5% of the mass of the lyocell fiber raw material by mass of silver nitrate.
Further, the coagulation bath solution in the step (3) is preferably an aqueous NMMO solution having a mass concentration of 5% to 15%.
Further, in the step (3), the alkali is sodium hydroxide, potassium hydroxide or ammonia water. And adding alkali to adjust the pH value to 9-13.
Further, the spinning in the step (4) refers to extruding and filtering the spinning solution through a screw extruder, then entering a spinning system, and ejecting the spinning solution through a spinneret plate to stretch and spin.
Further, the temperature of the solidification forming in the step (4) is 4-25 ℃.
And (3) further washing, oiling and drying the solidified and formed fiber in the step (4) to obtain the long-acting antibacterial flame-retardant double-effect lyocell fiber.
Furthermore, the water washing is to immerse the treated fibers in hot water at 70-90 ℃ for 3 min-2 h, wherein the bath ratio is 1: 10-30; the oiling refers to immersing the treated fibers into an oil bath solution, wherein the oil bath temperature is 80-90 ℃, the time is 3 min-2 h, and the bath ratio is 1: 10-30.
The long-acting antibacterial flame-retardant double-effect lyocell fiber is prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, ethylene diamine tetraacetic acid is used as a coupling agent to carry out covalent coupling modification on the lyocell fiber raw material and the flame retardant Provetex cp, so that the flame retardant effect is given to the fiber material on the basis of not reducing the mechanical property of the fiber; and a silver oxide antibacterial agent is introduced into the lyocell fiber, so that the antibacterial function modification of the lyocell fiber is realized, and the long-acting antibacterial flame-retardant double-effect lyocell fiber is obtained.
(2) According to the invention, the silver salt aqueous solution is added into the spinning solution, the alkali is added into the coagulating bath solution to adjust the pH value to be alkaline, and the antibacterial silver oxide is generated in situ in the fiber matrix in the process of coagulating and forming the spinning solution in the reactive coagulating bath after spinning, so that the antibacterial fiber has the advantages of uniform dispersion and strong adhesive force, and the obtained antibacterial fiber has a lasting antibacterial effect and is washable.
(3) The preparation method is simple, easy to industrialize and low in cost.
Drawings
FIG. 1 is a reaction scheme for the preparation of flame retardant modified lyocell fiber raw materials of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The long-acting antibacterial flame-retardant double-effect lyocell fiber is prepared by the following method:
(1) flame retardant modification of lyocell fiber raw materials: adding Provetex cp and ethylene diamine tetraacetic acid into a reactor according to the molar ratio of 2:1, stirring and reacting for 4 hours at 75 ℃, dehydrating in vacuum in the reaction process to promote the reaction, adding the lyocell fiber raw material cotton pulp after the reaction is finished, and continuing the esterification reaction to obtain a Provetex cp flame-retardant modified lyocell fiber raw material;
(2) preparation of spinning solution: dissolving the flame-retardant modified lyocell fiber raw material obtained in the step (1) in an N-methylmorpholine-N-oxide (NMMO) aqueous solution (obtained by carrying out reduced pressure distillation and concentration on about 50% of the commercially purchased NMMO aqueous solution) with the mass concentration of 90%, then adding a silver nitrate aqueous solution, wherein the addition amount of the silver nitrate aqueous solution is 0.5% of the mass of the lyocell fiber raw material by mass of silver nitrate, and uniformly stirring and mixing to obtain a spinning solution;
(3) preparation of reactive coagulation bath: adding sodium hydroxide into a 15% NMMO aqueous solution coagulating bath (obtained by diluting about 50% commercially available NMMO aqueous solution) to adjust the pH value to 11-12 to obtain a reactive coagulating bath;
(4) adding the spinning solution obtained in the step (2) into a screw extruder, further dissolving at 100 ℃, then filtering, and entering a spinning system, wherein the length of an air gap is 9cm, the spinning speed is 45m/min, the aperture of a spinneret plate is 80 microns, and the length of a pore capillary is 500 microns; and (3) vertically stretching the sprayed silk in the air, and carrying out solidification forming in the reactive solidification bath in the step (3), wherein the solidification forming temperature is 10 ℃. The treated fiber was immersed in hot water at 80 ℃ for 30min at a bath ratio of 1: 20. Then immersing into an oil bath solution, wherein the oil bath temperature is 85 ℃, the time is 30min, and the bath ratio is 1: 20. And finally, drying the fibers to obtain the long-acting antibacterial flame-retardant double-effect lyocell fibers.
Example 2
The long-acting antibacterial flame-retardant double-effect lyocell fiber is prepared by the following method:
(1) flame retardant modification of lyocell fiber raw materials: adding Provetex cp and ethylene diamine tetraacetic acid into a reactor according to the molar ratio of 2:1, stirring at 60 ℃ for reaction for 4 hours, carrying out vacuum dehydration in the reaction process to promote the reaction, adding a Lyocell fiber raw material wood pulp after the reaction is finished, and continuing the esterification reaction to obtain a Provetex cp flame-retardant modified Lyocell fiber raw material;
(2) preparation of spinning solution: dissolving the flame-retardant modified lyocell fiber raw material obtained in the step (1) in an N-methylmorpholine-N-oxide (NMMO) aqueous solution (obtained by carrying out reduced pressure distillation and concentration on about 50% of the commercially available NMMO aqueous solution) with the mass concentration of 95%, then adding a silver nitrate aqueous solution, wherein the addition amount of the silver nitrate aqueous solution is 1% of the mass of the lyocell fiber raw material in terms of the mass of silver nitrate, and uniformly stirring and mixing to obtain a spinning solution;
(3) preparation of reactive coagulation bath: adding potassium hydroxide into a 10% NMMO aqueous solution coagulating bath (obtained by diluting about 50% commercially available NMMO aqueous solution) to adjust the pH value to 10-11 to obtain a reactive coagulating bath;
(4) adding the spinning solution obtained in the step (2) into a screw extruder, further dissolving at 100 ℃, then filtering, and entering a spinning system, wherein the length of an air gap is 9cm, the spinning speed is 45m/min, the aperture of a spinneret plate is 80 microns, and the length of a pore capillary is 500 microns; and (3) vertically stretching the sprayed silk in the air, and carrying out solidification forming in the reactive solidification bath in the step (3), wherein the solidification forming temperature is 15 ℃. The treated fiber was immersed in hot water at 85 ℃ for 20min at a bath ratio of 1: 15. Then immersing into an oil bath solution, wherein the oil bath temperature is 90 ℃, the time is 20min, and the bath ratio is 1: 15. And finally, drying the fibers to obtain the long-acting antibacterial flame-retardant double-effect lyocell fibers.
Example 3
The long-acting antibacterial flame-retardant double-effect lyocell fiber is prepared by the following method:
(1) flame retardant modification of lyocell fiber raw materials: adding Provetex cp and ethylene diamine tetraacetic acid into a reactor according to the molar ratio of 2:1, stirring and reacting for 3h at 80 ℃, vacuum dehydrating in the reaction process to promote the reaction, adding the Lyocell fiber raw material bamboo pulp after the reaction is finished, and continuing the esterification reaction to obtain a Provetex cp flame-retardant modified Lyocell fiber raw material;
(2) preparation of spinning solution: dissolving the flame-retardant modified lyocell fiber raw material obtained in the step (1) in an N-methylmorpholine-N-oxide (NMMO) aqueous solution (obtained by carrying out reduced pressure distillation and concentration on about 50% of the commercially available NMMO aqueous solution) with the mass concentration of 95%, then adding a silver nitrate aqueous solution, wherein the addition amount of the silver nitrate aqueous solution is 2% of the mass of the lyocell fiber raw material in terms of the mass of silver nitrate, and uniformly stirring and mixing to obtain a spinning solution;
(3) preparation of reactive coagulation bath: adding ammonia water into a 5% NMMO aqueous solution coagulating bath (obtained by diluting about 50% commercially available NMMO aqueous solution) to adjust the pH value to 9-10 to obtain a reactive coagulating bath;
(4) adding the spinning solution obtained in the step (2) into a screw extruder, further dissolving at 100 ℃, then filtering, and entering a spinning system, wherein the length of an air gap is 9cm, the spinning speed is 45m/min, the aperture of a spinneret plate is 80 microns, and the length of a pore capillary is 500 microns; and (3) vertically stretching the sprayed silk in the air, and carrying out solidification forming in the reactive solidification bath in the step (3), wherein the solidification forming temperature is 25 ℃. The treated fiber was immersed in hot water at 85 ℃ for 60min at a bath ratio of 1: 20. Then immersing into an oil bath solution, wherein the oil bath temperature is 85 ℃, the time is 60min, and the bath ratio is 1: 20. And finally, drying the fibers to obtain the long-acting antibacterial flame-retardant double-effect lyocell fibers.
Example 4
The long-acting antibacterial flame-retardant lyocell fiber is prepared by the following method:
(1) flame retardant modification of lyocell fiber raw materials: adding Provetex cp and ethylene diamine tetraacetic acid into a reactor according to the molar ratio of 2:1, stirring and reacting for 4 hours at 70 ℃, vacuum dehydrating in the reaction process to promote the reaction, adding a Lyocell fiber raw material wood pulp after the reaction is finished, and continuing the esterification reaction to obtain a Provetex cp flame-retardant modified Lyocell fiber raw material;
(2) preparation of spinning solution: dissolving the flame-retardant modified lyocell fiber raw material obtained in the step (1) in an N-methylmorpholine-N-oxide (NMMO) aqueous solution (obtained by carrying out reduced pressure distillation and concentration on about 50% of the commercially available NMMO aqueous solution) with the mass concentration of 95%, then adding a silver nitrate aqueous solution, wherein the addition amount of the silver nitrate aqueous solution is 1% of the mass of the lyocell fiber raw material in terms of the mass of silver nitrate, and uniformly stirring and mixing to obtain a spinning solution;
(3) preparation of reactive coagulation bath: adding potassium hydroxide into a 10% NMMO aqueous solution coagulating bath (obtained by diluting about 50% commercially available NMMO aqueous solution) to adjust the pH value to 10-11 to obtain a reactive coagulating bath;
(4) adding the spinning solution obtained in the step (2) into a screw extruder, further dissolving at 100 ℃, then filtering, and entering a spinning system, wherein the length of an air gap is 9cm, the spinning speed is 45m/min, the aperture of a spinneret plate is 80 microns, and the length of a pore capillary is 500 microns; and (3) vertically stretching the sprayed silk in the air, and carrying out solidification forming in the reactive solidification bath in the step (3), wherein the solidification forming temperature is 15 ℃. The treated fiber was immersed in hot water at 85 ℃ for 20min at a bath ratio of 1: 15. Then immersing into an oil bath solution, wherein the oil bath temperature is 90 ℃, the time is 20min, and the bath ratio is 1: 15. And finally, drying the fiber to obtain the long-acting antibacterial flame-retardant lyocell fiber.
Comparative example 1
The antibacterial lyocell fiber of the comparative example is prepared by the following method:
(1) preparation of spinning solution: dissolving the lyocell fiber raw material wood pulp into 95% of N-methylmorpholine-N-oxide (NMMO) aqueous solution (obtained by carrying out reduced pressure distillation and concentration on about 50% of commercially available NMMO aqueous solution), adding nano silver oxide, stirring and mixing uniformly, wherein the adding amount of the nano silver oxide is 1% of the mass of the lyocell fiber raw material, and obtaining spinning solution;
(2) preparation of a coagulating bath: diluting about 50% of NMMO aqueous solution purchased commercially to the mass concentration of 10% to obtain a coagulating bath;
(3) adding the spinning solution obtained in the step (1) into a screw extruder, further dissolving at 100 ℃, then filtering, and entering a spinning system, wherein the length of an air gap is 9cm, the spinning speed is 45m/min, the aperture of a spinneret plate is 80 microns, and the length of a pore capillary is 500 microns; and (3) vertically stretching the sprayed silk in the air, and carrying out solidification forming in the solidification bath in the step (2) at a solidification forming temperature of 15 ℃. The treated fiber was immersed in hot water at 85 ℃ for 20min at a bath ratio of 1: 15. Then immersing into an oil bath solution, wherein the oil bath temperature is 90 ℃, the time is 20min, and the bath ratio is 1: 15. And finally, drying the fiber to obtain the bacteriostatic lyocell fiber.
Comparative example 2
The flame-retardant lyocell fiber of the comparative example is prepared by the following method:
(1) preparation of spinning solution: dissolving the lyocell fiber raw material wood pulp into 95% of N-methylmorpholine-N-oxide (NMMO) aqueous solution (obtained by carrying out reduced pressure distillation and concentration on about 50% of commercially available NMMO aqueous solution), adding an organic phosphorus flame retardant, stirring and mixing uniformly, wherein the adding amount of the organic phosphorus flame retardant is 3% of the mass of the lyocell fiber raw material, and obtaining a spinning solution;
(2) preparation of a coagulating bath: diluting about 50% of NMMO aqueous solution purchased commercially to the mass concentration of 10% to obtain a coagulating bath;
(3) adding the spinning solution obtained in the step (1) into a screw extruder, further dissolving at 100 ℃, then filtering, and entering a spinning system, wherein the length of an air gap is 9cm, the spinning speed is 45m/min, the aperture of a spinneret plate is 80 microns, and the length of a pore capillary is 500 microns; and (3) vertically stretching the sprayed silk in the air, and carrying out solidification forming in the solidification bath in the step (2) at a solidification forming temperature of 15 ℃. The treated fiber was immersed in hot water at 85 ℃ for 20min at a bath ratio of 1: 15. Then immersing into an oil bath solution, wherein the oil bath temperature is 90 ℃, the time is 20min, and the bath ratio is 1: 15. And finally, drying the fiber to obtain the flame-retardant lyocell fiber.
Comparative example 3
A lyocell fiber of this comparative example was prepared by the following method:
(1) preparation of spinning solution: dissolving lyocell fiber raw material wood pulp in 95% by mass of N-methylmorpholine-N-oxide (NMMO) aqueous solution (obtained by distilling and concentrating about 50% of commercially available NMMO aqueous solution under reduced pressure) to obtain spinning solution;
(2) preparation of a coagulating bath: diluting about 50% of NMMO aqueous solution purchased commercially to the mass concentration of 10% to obtain a coagulating bath;
(3) adding the spinning solution obtained in the step (1) into a screw extruder, further dissolving at 100 ℃, then filtering, and entering a spinning system, wherein the length of an air gap is 9cm, the spinning speed is 45m/min, the aperture of a spinneret plate is 80 mu m, and the length of a pore capillary is 500 mu m; and (3) vertically stretching the sprayed silk in the air, and carrying out solidification forming in the solidification bath in the step (2) at a solidification forming temperature of 15 ℃. The treated fiber was immersed in hot water at 85 ℃ for 20min at a bath ratio of 1: 15. Then immersing into an oil bath solution, wherein the oil bath temperature is 90 ℃, the time is 20min, and the bath ratio is 1: 15. And finally, drying the fiber to obtain the lyocell fiber.
The lyocell fibers obtained in the above examples 1-4 and comparative example 1 were tested for antibacterial properties, and the test bacteria were staphylococcus aureus and escherichia coli according to the "GB/T20944.3-2008 oscillation method". And the obtained antibacterial fiber is washed for 20 times and then tested for antibacterial performance again, and the test results are shown in the following table 1.
TABLE 1 antibacterial Properties and durable Wash resistance test results
As is apparent from the results in Table 1, the antibacterial silver oxide is generated in situ in the reactive coagulation bath, and the obtained antibacterial lyocell fiber has durable antibacterial effect and is washable.
The flame retardant performance of the lyocell fibers obtained in the above example 2 and comparative examples 2-3 is tested by an oxygen index test method, namely, the fibers are subjected to standard washing according to GB/T5454-1997 textile combustion performance test oxygen index method and GB/T20944.1-2007 washing fastness tester washing method. The test results are shown in table 2.
TABLE 2 flame retardancy test results
| Sample (I) | Initial limiting oxygen index (LOI,%) | Limiting oxygen index (LOI,%) after 20 washes |
| Example 2 | 30.3 | 27.2 |
| Comparative example 1 | 26.1 | 22.5 |
| Comparative example 2 | 21.2 | 17.9 |
As can be seen from the results in Table 2, the flame retardant modification of the lyocell fibers by the chemical coupling method achieves better and more durable flame retardant effect compared with the common physical blending method.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of long-acting antibacterial flame-retardant double-effect lyocell fiber is characterized by comprising the following preparation steps:
(1) adding Pyrovatex cp and ethylene diamine tetraacetic acid into a reactor, stirring at 60-80 ℃ for reaction, carrying out vacuum dehydration in the reaction process to promote the reaction, adding a lyocell fiber raw material after the reaction is finished, and continuing the esterification reaction to obtain a flame-retardant modified lyocell fiber raw material;
(2) preparation of spinning solution: dissolving the flame-retardant modified lyocell fiber raw material obtained in the step (1) in an NMMO (N-methyl-MO) aqueous solution, then adding a silver salt aqueous solution, and uniformly stirring and mixing to obtain a spinning solution;
(3) preparation of reactive coagulation bath: adding alkali into the coagulation bath solution to adjust the pH value to be alkaline, so as to obtain a reactive coagulation bath;
(4) and (3) spinning the spinning solution obtained in the step (2), and then allowing the spinning solution to enter the reactive coagulation bath obtained in the step (3) for coagulation forming to obtain the long-acting antibacterial flame-retardant double-effect lyocell fiber.
2. The preparation method of the long-acting antibacterial and flame-retardant double-effect lyocell fiber according to claim 1, which is characterized in that: the lyocell fiber raw material in the step (1) is hemp pulp, grass pulp, cotton pulp, wood pulp and bamboo pulp natural cellulose raw material.
3. The preparation method of the long-acting antibacterial and flame-retardant double-effect lyocell fiber according to claim 1, which is characterized in that: the molar ratio of the Pyrovatex cp to the ethylene diamine tetraacetic acid in the step (1) is 2:1, and the stirring reaction time is 3-4 h.
4. The preparation method of the long-acting antibacterial flame-retardant double-effect lyocell fiber according to claim 1 or 2, which is characterized in that: the mass concentration of the NMMO aqueous solution in the step (2) is 90-99%.
5. The preparation method of the long-acting antibacterial flame-retardant double-effect lyocell fiber according to claim 1 or 2, which is characterized in that: the silver salt aqueous solution in the step (2) is silver nitrate aqueous solution; the adding amount of the silver nitrate water solution is 0.2-5% of the mass of the lyocell fiber raw material by mass of silver nitrate.
6. The preparation method of the long-acting antibacterial flame-retardant double-effect lyocell fiber according to claim 1 or 2, which is characterized in that: the coagulating bath solution in the step (3) is an NMMO aqueous solution with the mass concentration of 5-15%; the alkali is sodium hydroxide, potassium hydroxide or ammonia water; and adding alkali to adjust the pH value to 9-13.
7. The preparation method of the long-acting antibacterial flame-retardant double-effect lyocell fiber according to claim 1 or 2, which is characterized in that: and (4) spinning refers to extruding and filtering the spinning solution through a screw extruder, then feeding the filtered spinning solution into a spinning system, and ejecting the filtered spinning solution through a spinneret plate to stretch and spin.
8. The preparation method of the long-acting antibacterial and flame-retardant double-effect lyocell fiber according to claim 1 or 2, which is characterized by comprising the following steps of: the temperature of the solidification forming in the step (4) is 4-25 ℃; and further washing, oiling and drying the solidified and formed fiber to obtain the long-acting antibacterial and flame-retardant double-effect lyocell fiber.
9. The preparation method of the long-acting antibacterial and flame-retardant double-effect lyocell fiber according to claim 8, which is characterized in that: the water washing is to immerse the treated fibers in hot water at the temperature of 70-90 ℃ for 3 min-2 h, wherein the bath ratio is 1: 10-30; the oiling refers to immersing the treated fibers into an oil bath solution, wherein the oil bath temperature is 80-90 ℃, the time is 3 min-2 h, and the bath ratio is 1: 10-30.
10. The long-acting antibacterial flame-retardant double-effect lyocell fiber is characterized in that: prepared by the method of any one of claims 1 to 9.
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| CN113862807B (en) * | 2021-10-25 | 2023-06-16 | 罗莱生活科技股份有限公司 | Flame-retardant lyocell filament and preparation method thereof |
| CN113957557B (en) * | 2021-11-08 | 2023-10-03 | 当阳市鸿阳新材料科技有限公司 | Efficient flame-retardant lyocell fiber and preparation method thereof |
| CN116005452A (en) * | 2022-12-29 | 2023-04-25 | 南通欧凯家用纺织品有限公司 | Preparation method of Tencel antibacterial and deodorant quilt cover fabric |
| CN117127394B (en) * | 2023-03-27 | 2025-07-15 | 和也健康科技有限公司 | Flame retardant and anti-ultraviolet fiber |
| CN116289179B (en) * | 2023-04-04 | 2024-10-18 | 和也健康科技有限公司 | Preparation method of functional fiber |
| CN117702296A (en) * | 2023-12-15 | 2024-03-15 | 江苏康溢臣生命科技有限公司 | Antibacterial cool sense lyocell fiber containing plant extracts and preparation method thereof |
| CN117966318B (en) * | 2024-01-04 | 2025-12-16 | 吴江京奕特种纤维有限公司 | Lyocell fiber vortex spun yarn and preparation method thereof |
| CN118497918B (en) * | 2024-07-18 | 2024-11-15 | 华东理工大学 | Preparation method and application of lyocell fiber containing chlorella component |
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