CN109402757B - Preparation method of anti-electromagnetic radiation lyocell fiber - Google Patents
Preparation method of anti-electromagnetic radiation lyocell fiber Download PDFInfo
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- CN109402757B CN109402757B CN201811245069.5A CN201811245069A CN109402757B CN 109402757 B CN109402757 B CN 109402757B CN 201811245069 A CN201811245069 A CN 201811245069A CN 109402757 B CN109402757 B CN 109402757B
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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
- D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/20—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen
- D06L4/27—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using organic agents
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Abstract
The invention relates to a method for preparing anti-electromagnetic radiation lyocell fiber, which is characterized by preparing polystyrene with a substance capable of reflecting electromagnetic radiation, and then dissolving the polystyrene and cotton pulp in N-methylmorpholine-N-oxide aqueous solution to prepare spinning solution; the spinning solution enters a spinning system, the sprayed silk threads are vertically stretched in the air and enter a coagulating bath groove to be coagulated into fibers; and the anti-electromagnetic radiation lyocell fiber is prepared by the processes of alcohol washing, bleaching, water washing, oiling, drying and the like. The main strength performance of the lyocell fiber prepared by the method is close to that of the lyocell fiber purchased in the market, and the lyocell fiber is qualified. The lyocell fiber prepared by the method is spun into lyocell fiber fabrics, the shielding rate ranges are respectively higher than 99%, and the shielding effectiveness ranges are respectively 26-32 dB. According to the GB/T26383-2011 shielding effectiveness requirement, the protection grade of the anti-electromagnetic radiation lyocell fiber prepared by the invention belongs to C grade, and the anti-electromagnetic radiation lyocell fiber has obvious anti-electromagnetic radiation performance.
Description
Technical Field
The invention belongs to the technical field of anti-electromagnetic radiation textiles, and particularly relates to a preparation method of anti-electromagnetic radiation lyocell fibers.
Background
The cellulose fiber prepared by using natural cellulose as a raw material and an organic solvent N-methylmorpholine-N-oxide (NMMO) spinning process is Lyocell (Lyocell) fiber according to the definition of the International rayon and synthetic fiber Bureau of standards (BISFA). The lyocell fiber raw material is renewable, has no pollution in the production link, has considerable social and economic benefits, and is called as novel low-carbon environment-friendly fiber with the most development potential in the 21 st century. Lyocell fibers have excellent properties such as hygroscopicity, dyeability, wearing comfort of natural fibers and high strength of synthetic fibers, and are ideal wearing fibers.
With the improvement of the social living standard, the requirements of people on textiles are higher and higher. Thus, various textiles with special functions have emerged, such as: textiles with special functions of radiation protection, antibiosis, water and oil resistance, unidirectional sweat conduction and the like are developed and successfully put into the market. Lyocell fiber, as a very excellent fiber material, exhibits excellent properties in all aspects, but it is still blank in the field of electromagnetic radiation prevention, and the disadvantages in this respect are to be further remedied. Regarding the health hazard caused by electromagnetic radiation, many countries have begun intensive research and published a great deal of research results, and most scientists believe that the diseases such as cataract, glaucoma, central nervous system dysfunction, female abortion, congenital malformation of offspring, leukemia, tumor and the like are caused by long-term electromagnetic radiation, but the mechanism of the diseases is not clear yet. Therefore, the harm of electromagnetic radiation cannot be ignored.
At present, there are many reports on the research of radiation-proof fabrics, such as: chinese patent application No. 200910088117.9 discloses an electromagnetic radiation resistant garment, wherein the yarn of the fabric comprises a core spun yarn, and the core spun yarn uses silver-plated fiber and the like as the core yarn. The comfort of the clothes prepared by the method is to be further improved due to the existence of the core-spun yarn. The Chinese patent application No. 201410742684.2 discloses an anti-electromagnetic radiation fabric coating adhesive and a preparation method thereof, wherein the anti-electromagnetic radiation fabric coating adhesive is prepared by preparing emulsion from styrene, acrylic acid and the like through polymerization reaction and then compounding with polyaniline and the like. However, after the fabric coating adhesive for preventing electromagnetic radiation is washed for many times, the coating adhesive may be washed away, and thus, the electromagnetic radiation resistance of the fabric may be weakened. In general, the radiation protective fabric is prepared by the following four methods: (1) weaving the metal wire and the yarn together; (2) spinning metal fibers into the yarn; (3) the metallized fiber using metallized fiber means a fiber having a surface on which a conductive film is formed by a coating or plating method; (4) bulk conductive monomers and polymers were developed. The four methods can be tried to ensure that the lyocell fiber has the performance of preventing electromagnetic radiation, but due to the special structure of the lyocell fiber, the difficulty of realizing the performance of preventing electromagnetic radiation by adopting the four methods is very high under the condition of not damaging the special performance of the lyocell fiber, and a new method needs to be found.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of anti-electromagnetic radiation lyocell fiber. The invention mixes a substance which can reflect the electromagnetic radiation into the cellulose fiber, the substance is polystyrene, the polystyrene can reflect the electromagnetic radiation by virtue of low resistance and conductivity, and the current and magnetic polarization which are opposite to the original electromagnetic radiation are generated in the conductor to form a shielding space, thereby weakening the harm of the external electromagnetic radiation.
The invention discloses a preparation method of anti-electromagnetic radiation lyocell fiber, which is characterized by comprising the following steps:
(1) preparation of polystyrene: sequentially adding reagents including styrene, benzyl chloride, cuprous chloride and 2, 2 '-bipyridyl according to a designed amount into a four-mouth bottle, wherein the ratio of the styrene (mL), the benzyl chloride (mL), the cuprous chloride (g) and the 2, 2' -bipyridyl (g) is 50-100: 5-10: 1-3; vacuumizing the mixture for 30-60 min under-250-1000 Pa in an ice salt bath, then heating to room temperature, introducing nitrogen, and repeating the steps for three times; under the protection of nitrogen, a condenser, a thermometer and a stirrer are arranged, the temperature is raised to 60-80 ℃ for reaction, the reaction time is 3-4 hours, methanol with the volume 5-10 times that of the mixed solution is added to separate out a precipitate, and the precipitate is filtered, namely polystyrene; testing of polystyrene molecular weight: the molecular weight and the molecular weight distribution of the polymer are measured by a Waters 510 high performance liquid chromatograph, polystyrene is used as a standard sample, and THF is used as a mobile phase; measuring the Mn of the polystyrene to be 5000-20000 and the distribution index (Mw/Mn) to be 1.20-1.50;
(2) preparing a spinning solution: distilling 49-54% by mass of an NMMO aqueous solution under reduced pressure to 82-92% by mass of an NMMO aqueous solution, dissolving the polystyrene and cotton pulp meal (produced by Shandong silver eagle chemical fiber Co., Ltd.) prepared in the step (1) in the NMMO aqueous solution, wherein the mass ratio of the polystyrene to the cotton pulp meal is 1: 25-35, the bath ratio of the mass (g) of the cotton pulp meal to the volume (mL) of the NMMO aqueous solution is 1: 12-16, and stirring and dissolving the mixture in a reaction kettle at 115-130 ℃ for 3-5 hours in vacuum to prepare a uniform spinning solution with the mass fraction of 12-15%;
(3) spinning of lyocell fibers: adding the spinning solution treated in the step (2) into a screw extruder, further dissolving at 96-115 ℃, then filtering, and entering a spinning system, wherein the length of an air gap is 7-9 cm, the spinning speed is 35-55 m/min, the pore diameter of a spinneret plate is 15-115 mu m, and the length of a pore capillary is 350-800 mu m; the sprayed silk threads are vertically stretched in the air, enter a coagulating bath, and are coagulated and formed, wherein the concentration of NMMO (N-methyl-amino-methyl-N-methyl-ammonium) water solution in the coagulating bath is 10-14%, and the temperature of the coagulating bath is 0-14 ℃; the flow chart of the lyocell fiber spinning equipment is shown in figure 1;
(4) alcohol washing of the fibers: immersing the fiber treated in the step (3) into an ethanol solution with the concentration of 85-92% for 3-5 hours, wherein the solution temperature is room temperature, and the bath ratio is 1: 12-16;
(5) bleaching the fiber: immersing the fiber treated in the step (4) into a bleaching agent solution (the name is strong chlorine essence, produced by Shandong Jia clean water treatment science and technology Limited) with the concentration of 0.1-0.3 g/L for 3-4 hours, wherein the temperature of the solution is 50-55 ℃, and the bath ratio is 1: 24-28;
(6) and (3) water washing of the fiber: immersing the fibers treated in the step (5) into hot water at the temperature of 70-85 ℃ for 3-4 hours at a bath ratio of 1: 20-25;
(7) oiling the fibers: immersing the fibers treated in the step (6) into 3-4 g/L of oil bath solution (model: HY-101, produced by Hangzhou Huaya chemical industry Co., Ltd.), wherein the oil bath temperature is 80-85 ℃, the time is 3-4 hours, and the bath ratio is 1: 15-20;
(8) drying the fibers: and (4) drying the fiber treated in the step (7) to obtain the anti-electromagnetic radiation lyocell fiber.
The invention has the following remarkable characteristics:
(1) the dry breaking strength of the anti-electromagnetic radiation lyocell fiber prepared by the method is 42-43 cN/tex, and the dry breaking elongation is 13-14.5%; the wet breaking strength of the anti-electromagnetic radiation lyocell fiber is between 26 and 28cN/tex, the wet breaking elongation of the fiber is between 16.5 and 17.5 percent, and the main strength performance of the anti-electromagnetic radiation lyocell fiber is close to that of the lyocell fiber purchased in the market. The cellulose fiber prepared by the invention is qualified lyocell fiber.
(2) The shielding rate range of the anti-electromagnetic radiation lyocell fabric prepared by the method is higher than 99%, and the shielding effectiveness range is distributed in 26-32 dB. According to the GB/T26383-2011 shielding effectiveness requirement, the protection grade of the anti-electromagnetic radiation lyocell fiber prepared by the invention belongs to C grade, and the anti-electromagnetic radiation lyocell fiber has obvious anti-electromagnetic radiation performance. After the lyocell fiber prepared by the method is washed for 20 times, the protection grade still belongs to grade C.
(3) The invention adopts NMMO to dissolve cellulose and polystyrene at the same time, and then the cellulose and the polystyrene are spun to prepare the lyocell fiber. Polystyrene generates a reflection effect on electromagnetic radiation by virtue of low resistance and conductivity, and generates current and magnetic polarization opposite to the original electromagnetic radiation in the conductor to form a shielding space, so that the harm of external electromagnetic radiation is reduced. The lyocell fiber prepared by the preparation method has strong electromagnetic radiation resistance, simple whole production process, low price and small environmental pollution in the production process.
Drawings
FIG. 1 shows a flow diagram of a lyocell fiber spinning apparatus (1. spinning fluid; 2. godet; 3. coagulation bath; 4. godet; 5. winding roll; 6. spinneret; 7. guide tube; 8. metering pump; 9. static mixer; 10. filter; 11. metering zone; 12. vent hole; 13. screw; 14. hopper; 15. stirring blade; 16. suspension)
Detailed Description
The examples described below illustrate the invention in detail.
Example 1
The preparation method of the anti-electromagnetic radiation lyocell fiber comprises the following steps:
(1) preparation of polystyrene: adding reagents including styrene, benzyl chloride, cuprous chloride and 2, 2 '-bipyridyl into a four-mouth bottle in sequence according to a design amount, wherein the dosage of the styrene, the benzyl chloride, the cuprous chloride and the 2, 2' -bipyridyl is 50mL, 5mL, 1g and 1g respectively. It was evacuated under-250 Pa for 30min under an ice salt bath, then warmed to room temperature and purged with nitrogen, and so on three times. Under the protection of nitrogen, a condenser, a thermometer and a stirrer are arranged, the temperature is raised to 60 ℃ for reaction, the reaction time is 3 hours, methanol with 5 times of the volume of the mixed solution is added to separate out the precipitate, and the precipitate is filtered, namely the polystyrene. Testing of polystyrene molecular weight: the molecular weight and molecular weight distribution of the polymer were determined by means of a Waters model 510 high performance liquid chromatograph, polystyrene as standard and THF as mobile phase. It was found that the polystyrene had Mn of 12500 and a distribution index (Mw/Mn) of 1.36.
(2) Preparing a spinning solution: distilling 51.9% by mass of NMMO aqueous solution under reduced pressure to 85% by mass of NMMO aqueous solution, dissolving the polystyrene and cotton pulp meal (produced by Shandong Yingying chemical fiber Co., Ltd.) prepared in the step (1) in the NMMO aqueous solution, wherein the mass ratio of the polystyrene to the cotton pulp meal is 1: 25, the bath ratio of the mass (g) of the cotton pulp meal to the volume (mL) of the NMMO aqueous solution is 1: 12, and stirring and dissolving in a reaction kettle at 120 ℃ for 4 hours under vacuum to prepare the uniform spinning solution with the mass fraction of 13%.
(3) Spinning of lyocell fibers: adding the spinning solution treated in the step (2) into a screw extruder, further dissolving at 105 ℃, then filtering, and entering a spinning system, wherein the length of an air gap is 8cm, the spinning speed is 35m/min, the aperture of a spinneret plate is 105 mu m, and the length of a pore capillary is 400 mu m; the sprayed silk threads are vertically stretched in the air, enter a coagulating bath, and are coagulated and formed, wherein the concentration of the coagulating bath is 11 percent of NMMO aqueous solution, and the temperature of the coagulating bath is 5 ℃. The flow chart of the lyocell fiber spinning equipment is shown in figure 1.
(4) Alcohol washing of the fibers: immersing the fiber treated in the step (3) into 86% ethanol solution at room temperature for 4 hours at a bath ratio of 1: 12.
(5) Bleaching the fiber: and (3) immersing the fiber treated in the step (4) into a bleaching agent solution (name: strong chlorine essence, produced by Shandong Jia clean water treatment science and technology Limited) with the concentration of 0.15g/L for 3.5 hours at the temperature of 55 ℃ and the bath ratio of 1: 25.
(6) And (3) water washing of the fiber: soaking the fiber treated in step (5) in 75 deg.C hot water for 3 hr at a bath ratio of 1: 20.
(7) Oiling the fibers: immersing the fiber treated in the step (6) into 3g/L oil bath solution (model: HY-101, produced by Hangzhou Huaya chemical Co., Ltd.) at 80 deg.C for 3 hr at a bath ratio of 1: 15.
(8) Drying the fibers: and (4) drying the fiber treated in the step (7) to obtain the anti-electromagnetic radiation lyocell fiber a.
Example 2
The preparation method of the anti-electromagnetic radiation lyocell fiber comprises the following steps:
(1) preparation of polystyrene: adding reagents including styrene, benzyl chloride, cuprous chloride and 2, 2 '-bipyridyl into a four-mouth bottle in sequence according to a design amount, wherein the dosage proportion relation of the styrene, the benzyl chloride, the cuprous chloride and the 2, 2' -bipyridyl is 60mL, 6mL, 2g and 2 g. It is vacuumed at-800 Pa for 35min under ice salt bath, then warmed to room temperature, purged with nitrogen, and so on for three times. Under the protection of nitrogen, a condenser, a thermometer and a stirrer are arranged, the temperature is raised to 70 ℃ for reaction, the reaction time is 3.5 hours, methanol with 6 times of the volume of the mixed solution is added to separate out the precipitate, and the precipitate is filtered, namely the polystyrene. Testing of polystyrene molecular weight: the molecular weight and molecular weight distribution of the polymer were determined by means of a Waters model 510 high performance liquid chromatograph, polystyrene as standard and THF as mobile phase. It was found that the polystyrene had Mn of 13600 and a distribution index (Mw/Mn) of 1.42.
(2) Preparing a spinning solution: distilling 53.1% by mass of NMMO aqueous solution under reduced pressure to 90% by mass of NMMO aqueous solution, dissolving the polystyrene and cotton pulp meal (produced by Shandong Yingying chemical fiber Co., Ltd.) prepared in the step (1) in the NMMO aqueous solution, wherein the mass ratio of the polystyrene to the cotton pulp meal is 1: 30, the bath ratio of the mass (g) of the cotton pulp meal to the volume (mL) of the NMMO aqueous solution is 1: 14, and stirring and dissolving in a reaction kettle at 120 ℃ for 5 hours under vacuum to prepare 14% by mass of uniform spinning solution.
(3) Spinning of lyocell fibers: adding the spinning solution treated in the step (2) into a screw extruder, further dissolving at 105 ℃, then filtering, and entering a spinning system, wherein the length of an air gap is 9cm, the spinning speed is 55m/min, the aperture of a spinneret plate is 115 mu m, and the length of a pore capillary is 500 mu m; the sprayed silk threads are vertically stretched in the air, enter a coagulating bath, and are coagulated and formed, wherein the concentration of the coagulating bath is 13 percent of NMMO aqueous solution, and the temperature of the coagulating bath is 8 ℃. The flow chart of the lyocell fiber spinning equipment is shown in figure 1.
(4) Alcohol washing of the fibers: immersing the fiber treated in the step (3) into 90% ethanol solution at room temperature for 3.5 hr at a bath ratio of 1: 15.
(5) Bleaching the fiber: and (3) immersing the fiber treated in the step (4) into a bleaching agent solution (name: strong chlorine essence, produced by Shandong Jia clean water treatment science and technology Limited) with the concentration of 0.15g/L for 3.5 hours at the temperature of 53 ℃ and the bath ratio of 1: 28.
(6) And (3) water washing of the fiber: soaking the fiber treated in the step (5) in hot water at 85 deg.C for 3 hr at a bath ratio of 1: 20.
(7) Oiling the fibers: immersing the fiber treated in the step (6) into 3g/L oil bath solution (model: HY-101, produced by Hangzhou Huaya chemical Co., Ltd.) at 80 deg.C for 3 hr at a bath ratio of 1: 15.
(8) Drying the fibers: and (4) drying the fiber treated in the step (7) to obtain the anti-electromagnetic radiation lyocell fiber b.
Example 3
The preparation method of the anti-electromagnetic radiation lyocell fiber comprises the following steps:
(1) preparation of polystyrene: adding reagents including styrene, benzyl chloride, cuprous chloride and 2, 2 '-bipyridyl into a four-mouth bottle in sequence according to a design amount, wherein the dosage proportion relation of the styrene, the benzyl chloride, the cuprous chloride and the 2, 2' -bipyridyl is 70mL, 7mL, 3g and 3 g. It was evacuated under ice salt bath at-900 Pa for 40min, then warmed to room temperature and purged with nitrogen, and so on three times. Under the protection of nitrogen, a condenser, a thermometer and a stirrer are arranged, the temperature is raised to 70 ℃ for reaction, the reaction time is 3.5 hours, methanol with 7 times of the volume of the mixed solution is added to separate out the precipitate, and the precipitate is filtered, namely the polystyrene. Testing of polystyrene molecular weight: the molecular weight and molecular weight distribution of the polymer were determined by means of a Waters model 510 high performance liquid chromatograph, polystyrene as standard and THF as mobile phase. It was found that the polystyrene had Mn of 17600 and a distribution index (Mw/Mn) of 1.48.
(2) Preparing a spinning solution: distilling 52.5% by mass of NMMO aqueous solution under reduced pressure to 90% by mass of NMMO aqueous solution, dissolving the polystyrene and cotton pulp meal (produced by Shandong Yingying chemical fiber Co., Ltd.) prepared in the step (1) in the NMMO aqueous solution, wherein the mass ratio of the polystyrene to the cotton pulp meal is 1: 30, the bath ratio of the mass (g) of the cotton pulp meal to the volume (mL) of the NMMO aqueous solution is 1: 13, and stirring and dissolving in a reaction kettle at 120 ℃ for 5 hours under vacuum to prepare 14% by mass of uniform spinning solution.
(3) Spinning of lyocell fibers: adding the spinning solution treated in the step (2) into a screw extruder, further dissolving at 96-115 ℃, then filtering, and entering a spinning system, wherein the length of an air gap is 8cm, the spinning speed is 855m/min, the aperture of a spinneret plate is 105 μm, and the length of a pore capillary is 380 μm; the sprayed silk threads are vertically stretched in the air, enter a coagulating bath, and are coagulated and formed, wherein the concentration of the coagulating bath is 13 percent of NMMO aqueous solution, and the temperature of the coagulating bath is 9 ℃. The flow chart of the lyocell fiber spinning equipment is shown in figure 1.
(4) Alcohol washing of the fibers: immersing the fiber treated in the step (3) into 90% ethanol solution at room temperature for 3.5 hr at a bath ratio of 1: 15.
(5) Bleaching the fiber: and (3) immersing the fiber treated in the step (4) into a bleaching agent solution (name: strong chlorine essence, produced by Shandong Jia clean water treatment science and technology Limited) with the concentration of 0.3g/L for 3.5 hours at the temperature of 55 ℃ and the bath ratio of 1: 28.
(6) And (3) water washing of the fiber: soaking the fiber treated in the step (5) in hot water at 80 ℃ for 3 hours at a bath ratio of 1: 22.
(7) Oiling the fibers: immersing the fiber treated in the step (6) into 3.5g/L oil bath solution (model: HY-101, produced by Hangzhou Huaya chemical Co., Ltd.) at 80 deg.C for 3 hr at a bath ratio of 1: 18.
(8) Drying the fibers: and (4) drying the fiber treated in the step (7) to obtain the anti-electromagnetic radiation lyocell fiber c.
Example 4
The preparation method of the anti-electromagnetic radiation lyocell fiber comprises the following steps:
(1) preparation of polystyrene: adding reagents including styrene, benzyl chloride, cuprous chloride and 2, 2 '-bipyridyl into a four-mouth bottle in sequence according to a design amount, wherein the dosage proportion relation of the styrene, the benzyl chloride, the cuprous chloride and the 2, 2' -bipyridyl is 80mL, 8mL, 3g and 3 g. It was evacuated under ice salt bath at-900 Pa for 60min, then warmed to room temperature and purged with nitrogen, and so on three times. Under the protection of nitrogen, a condenser, a thermometer and a stirrer are arranged, the temperature is increased to 75 ℃ for reaction, the reaction time is 3 hours, methanol with the volume 9 times that of the mixed solution is added to separate out the precipitate, and the precipitate is filtered, namely the polystyrene. Testing of polystyrene molecular weight: the molecular weight and molecular weight distribution of the polymer were determined by means of a Waters model 510 high performance liquid chromatograph, polystyrene as standard and THF as mobile phase. It was found that the polystyrene had Mn of 17900 and a distribution index (Mw/Mn) of 1.29.
(2) Preparing a spinning solution: distilling 53.4% by mass of NMMO aqueous solution under reduced pressure to 86% by mass of NMMO aqueous solution, dissolving the polystyrene and cotton pulp meal (produced by Shandong Yingying chemical fiber Co., Ltd.) prepared in the step (1) in the NMMO aqueous solution, wherein the mass ratio of the polystyrene to the cotton pulp meal is 1: 30, the bath ratio of the mass (g) of the cotton pulp meal to the volume (mL) of the NMMO aqueous solution is 1: 15, and stirring and dissolving in a reaction kettle at 120 ℃ in vacuum for 3 hours to prepare the uniform spinning solution with the mass fraction of 15%.
(3) Spinning of lyocell fibers: adding the spinning solution treated in the step (2) into a screw extruder, further dissolving at 115 ℃, filtering, and entering a spinning system, wherein the length of an air gap is 9cm, the spinning speed is 55m/min, the aperture of a spinneret plate is 100 mu m, and the length of a pore capillary is 700 mu m; the sprayed silk threads are vertically stretched in the air, enter a coagulating bath, and are coagulated and formed, wherein the concentration of the coagulating bath is 12 percent of NMMO aqueous solution, and the temperature of the coagulating bath is 10 ℃. The flow chart of the lyocell fiber spinning equipment is shown in figure 1.
(4) Alcohol washing of the fibers: immersing the fiber treated in the step (3) into 88% ethanol solution at room temperature for 4 hours at a bath ratio of 1: 16.
(5) Bleaching the fiber: and (3) immersing the fiber treated in the step (4) into a bleaching agent solution (name: strong chlorine essence, produced by Shandong Jia clean water treatment science and technology Limited) with the concentration of 0.3g/L for 4 hours at the temperature of 55 ℃ at the bath ratio of 1: 24.
(6) And (3) water washing of the fiber: soaking the fiber treated in the step (5) in hot water at 85 deg.C for 4 hr at a bath ratio of 1: 25.
(7) Oiling the fibers: immersing the fiber treated in the step (6) into 4g/L oil bath solution (model: HY-101, produced by Hangzhou Huaya chemical Co., Ltd.) at 85 deg.C for 4 hr at a bath ratio of 1: 20.
(8) Drying the fibers: and (4) drying the fiber treated in the step (7) to obtain the anti-electromagnetic radiation lyocell fiber d.
Example 5
The preparation method of the anti-electromagnetic radiation lyocell fiber comprises the following steps:
(1) preparation of polystyrene: adding reagents including styrene, benzyl chloride, cuprous chloride and 2, 2 '-bipyridyl into a four-mouth bottle in sequence according to a design amount, wherein the dosage proportion relation of the styrene, the benzyl chloride, the cuprous chloride and the 2, 2' -bipyridyl is 100mL, 10mL, 3g and 3 g. It was evacuated under-1000 Pa for 60min under an ice salt bath, then warmed to room temperature and purged with nitrogen, and so on three times. Under the protection of nitrogen, a condenser, a thermometer and a stirrer are arranged, the temperature is increased to 80 ℃ for reaction, the reaction time is 4 hours, methanol with 10 times of the volume of the mixed solution is added to separate out the precipitate, and the precipitate is filtered, namely the polystyrene. Testing of polystyrene molecular weight: the molecular weight and molecular weight distribution of the polymer were determined by means of a Waters model 510 high performance liquid chromatograph, polystyrene as standard and THF as mobile phase. It was found that the polystyrene had Mn of 19500 and a distribution index (Mw/Mn) of 1.48.
(2) Preparing a spinning solution: distilling the NMMO aqueous solution with the mass fraction of 50.1% to the NMMO aqueous solution with the mass fraction of 92%, dissolving the polystyrene and cotton pulp meal (produced by Shandong Yingying chemical fiber Co., Ltd.) prepared in the step (1) in the NMMO aqueous solution, wherein the mass ratio of the polystyrene to the cotton pulp meal is 1: 35, the bath ratio of the mass (g) of the cotton pulp meal to the volume (mL) of the NMMO aqueous solution is 1: 12, and stirring and dissolving the mixture in a reaction kettle at 130 ℃ in vacuum for 5 hours to prepare the uniform spinning solution with the mass fraction of 15%.
(3) Spinning of lyocell fibers: adding the spinning solution treated in the step (2) into a screw extruder, further dissolving at 115 ℃, then filtering, and entering a spinning system, wherein the length of an air gap is 7cm, the spinning speed is 55m/min, the aperture of a spinneret plate is 50 mu m, and the length of a pore capillary is 600 mu m; the sprayed silk threads are vertically stretched in the air, enter a coagulating bath, and are coagulated and formed, wherein the concentration of the coagulating bath is 11 percent of NMMO aqueous solution, and the temperature of the coagulating bath is 7 ℃. The flow chart of the lyocell fiber spinning equipment is shown in figure 1.
(4) Alcohol washing of the fibers: immersing the fiber treated in the step (3) into an ethanol solution with the concentration of 85% for 3 hours, wherein the solution temperature is room temperature, and the bath ratio is 1: 12.
(5) Bleaching the fiber: and (3) immersing the fiber treated in the step (4) into a bleaching agent solution (name: strong chlorine essence, produced by Shandong Jia clean water treatment science and technology Limited) with the concentration of 0.1g/L for 3 hours at the temperature of 55 ℃ at the bath ratio of 1: 24.
(6) And (3) water washing of the fiber: soaking the fiber treated in step (5) in 70 deg.C hot water for 3 hr at a bath ratio of 1: 22.
(7) Oiling the fibers: immersing the fiber treated in the step (6) into 3.5g/L oil bath solution (model: HY-101, produced by Hangzhou Huaya chemical Co., Ltd.) at 80 deg.C for 3 hr at a bath ratio of 1: 18.
(8) Drying the fibers: and (4) drying the fiber treated in the step (7) to obtain the anti-electromagnetic radiation lyocell fiber e.
Performance evaluation examples:
the strength performance of the anti-electromagnetic radiation lyocell fibers a, b, c, d and e prepared in the above specific embodiments 1 to 5 of the present invention is tested, and the test method refers to GB/T-24218.3-2010 part 3 of the test method for textiles and non-woven fabrics: determination of breaking strength and breaking elongation, a FAVIMAT-BOBOBOT 2 full-automatic single fiber universal tester is adopted to determine the strength performance of the test samples, no less than 30 test samples are tested, and the test average value is taken. The test results are shown in table 1, wherein the anti-electromagnetic radiation lyocell fibers a, b, c, d, e are abbreviated as fibers a, b, c, d, e, and the lyocell fibers purchased from seould danao textile limited.
TABLE 1 mechanical Properties of radiation protection Lyocell fibers a, b, c, d, e and procured Lyocell fibers
| Item | Fiber a | Fiber b | Fiber c | Fibre d | Fibers e | Purchased lyocell fibre |
| Dry breaking Strength (cN/tex) | 42.7 | 42.6 | 42.2 | 42.8 | 42.1 | 47.3 |
| Elongation at Dry Break (%) | 13.7 | 14.2 | 14.5 | 14.3 | 13.4 | 12.9 |
| Wet tensile Strength (cN/tex) | 27.5 | 27.4 | 27.1 | 26.8 | 27.8 | 35.2 |
| Wet elongation at break (%) | 17.2 | 17.3 | 17.2 | 16.8 | 16.9 | 14.1 |
As can be seen from Table 1, the dry breaking strength of the anti-electromagnetic radiation lyocell fiber is 42-43 cN/tex and is slightly lower than that of the purchased lyocell fiber, and the dry breaking elongation of the anti-electromagnetic radiation lyocell fiber is 13-14.5% and is slightly higher than that of the purchased lyocell fiber; the wet breaking strength of the anti-electromagnetic radiation lyocell fiber is between 26 and 28cN/tex, which is lower than that of the purchased lyocell fiber, and the wet breaking elongation of the anti-electromagnetic radiation lyocell fiber is between 16.5 and 17.5 percent, which is slightly higher than that of the purchased lyocell fiber. From the test result of mechanical properties, the main mechanical properties of the anti-electromagnetic radiation lyocell fiber prepared by the method are closer to those of lyocell fibers of Shaoxing Danao textile Co., Ltd, so that the cellulose fiber prepared by the method is qualified lyocell fiber.
In order to better detect the electromagnetic radiation resistance of the anti-electromagnetic radiation lyocell fibers prepared in the present invention, the anti-electromagnetic radiation lyocell fibers a, b, c, d, and e prepared in the above embodiments 1 to 5 of the present invention and the purchased lyocell fibers are spun into anti-electromagnetic radiation lyocell fabric a, b, c, d, and e (fabric a, b, c, d, and e for short) and purchased lyocell fabric by using the same process. Referring to a specific test method of GB/T22583-2009 radiation protection knitwear, at least 20 test samples are taken, a test average value is taken, and test results are shown in Table 2.
TABLE 2 Shielding effectiveness of anti-electromagnetic radiation lyocell fabrics a, b, c, d, e and procured lyocell fabrics
As can be seen from table 2, the shielding rate ranges of the electromagnetic radiation preventing lyocell fabrics a, b, c, d, e are all higher than 99%, while the shielding rate of the purchased lyocell fabric is only 18.7%. The shielding effectiveness range of the electromagnetic radiation preventing lyocell fabrics a, b, c, d and e is distributed in the range of 26-32 dB, and the shielding effectiveness of the purchased lyocell fabrics is only 5.66 dB. According to the GB/T26383-2011 shielding effectiveness requirement (shown in table 3), the fabric prepared by the invention has the electromagnetic radiation prevention performance. The lyocell fibers produced according to the present invention were rated as class C according to the requirements of table 3.
TABLE 3 GB/T26383-2011 Shielding effectiveness requirements
In order to better detect the influence of washing on the anti-electromagnetic radiation performance of the lyocell fiber prepared in the invention, the lyocell fiber fabrics a, b, c, d and e with anti-electromagnetic radiation are subjected to standard washing by referring to a washing method of a GB/T20944.1-2007 color fastness to washing machine, and after being washed for 20 times, the anti-electromagnetic radiation performance of the lyocell fiber fabrics is tested again, and the test results are shown in Table 4.
TABLE 4 Shielding effectiveness of anti-electromagnetic radiation lyocell fabrics a, b, c, d, e after 20 washes
It can be seen from table 4 that after 20 times of water washing, the shielding rate ranges of the electromagnetic radiation resistant lyocell fabrics a, b, c, d and e are still higher than 99%; the shielding effectiveness range of the electromagnetic radiation preventing lyocell fabrics a, b, c, d and e is 23-30 dB. According to the shield effectiveness requirement of GB/T26383-2011 (shown in table 3), the protection grade of the lyocell fiber prepared by the invention still belongs to the C grade after 20 times of water washing.
Claims (8)
1. A preparation method of anti-electromagnetic radiation lyocell fiber is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of polystyrene: sequentially adding reagents of styrene, benzyl chloride, cuprous chloride and 2, 2' -bipyridyl into a four-mouth bottle according to the designed amount; vacuumizing the mixture for 30-60 min under-250 to-1000 Pa in an ice salt bath, then heating to room temperature, introducing nitrogen, and repeating the steps for three times; under the protection of nitrogen, a condenser, a thermometer and a stirrer are arranged, the temperature is raised to 60-80 ℃ for reaction, the reaction time is 3-4 hours, methanol with the volume 5-10 times that of the mixed solution is added to separate out a precipitate, and the precipitate is filtered, namely polystyrene; testing of polystyrene molecular weight: measuring the molecular weight and molecular weight distribution of the polymer by using a high performance liquid chromatograph, wherein polystyrene is used as a standard sample, and THF is used as a mobile phase; measuring Mn of the polystyrene to be 5000-20000, and the distribution index Mw/Mn to be 1.20-1.50;
(2) preparing a spinning solution: distilling 49-54% by mass of an N-methylmorpholine-N-oxide aqueous solution under reduced pressure to 82-92%, dissolving the polystyrene and cotton pulp meal prepared in the step (1) in the N-methylmorpholine-N-oxide aqueous solution, wherein the bath ratio of the mass of the cotton pulp meal to the volume of the N-methylmorpholine-N-oxide aqueous solution is 1 g: 12-16 mL, and stirring and dissolving in a reaction kettle at 115-130 ℃ in vacuum for 3-5 hours to prepare a uniform spinning solution, wherein the mass fraction of the spinning solution is 12-15%;
(3) spinning of lyocell fibers: adding the spinning solution treated in the step (2) into a screw extruder, further dissolving at 96-115 ℃, then filtering, and entering a spinning system, wherein the length of an air gap, the spinning speed, the aperture of a spinneret plate and the length of a capillary tube with holes are set to be proper values; the sprayed silk threads are vertically stretched in the air, enter a coagulating bath, and are coagulated and formed, wherein the coagulating bath is 10-14% of N-methylmorpholine-N-oxide aqueous solution at a proper temperature;
(4) alcohol washing of the fibers: immersing the fiber treated in the step (3) into an ethanol solution with a certain concentration for 3-5 hours at room temperature, wherein the bath ratio is 1: 12-16;
(5) bleaching the fiber: immersing the fiber treated in the step (4) into a bleaching agent solution with a certain concentration for 3-4 hours at the temperature of 50-55 ℃ at a bath ratio of 1: 24-28;
(6) and (3) water washing of the fiber: immersing the fibers treated in the step (5) into hot water at the temperature of 70-85 ℃ for 3-4 hours at a bath ratio of 1: 20-25;
(7) oiling the fibers: immersing the fibers treated in the step (6) into an oil bath solution with a certain concentration, wherein the oil bath temperature is 80-85 ℃, the time is 3-4 hours, and the bath ratio is 1: 15-20;
(8) drying the fibers: and (4) drying the fiber treated in the step (7) to obtain the anti-electromagnetic radiation lyocell fiber.
2. The method for preparing the lyocell fiber for preventing electromagnetic radiation according to claim 1, wherein the method comprises the following steps: the dosage proportion relation of the styrene, the benzyl chloride, the cuprous chloride and the 2, 2' -bipyridine in the step (1) is 50-100 mL: 5-10 mL: 1-3 g.
3. The method for preparing the lyocell fiber for preventing electromagnetic radiation according to claim 1, wherein the method comprises the following steps: the mass ratio of the polystyrene to the cotton pulp meal in the step (2) is 1: 25-35.
4. The method for preparing the lyocell fiber for preventing electromagnetic radiation according to claim 1, wherein the method comprises the following steps: and (3) the length of the air gap is 7-9 cm, the spinning speed is 35-55 m/min, the aperture of the spinneret plate is 15-115 mu m, and the length of the capillary tube is 350-800 mu m.
5. The method for preparing the lyocell fiber for preventing electromagnetic radiation according to claim 1, wherein the method comprises the following steps: the temperature of the coagulation bath in the step (3) is 0-14 ℃.
6. The method for preparing the lyocell fiber for preventing electromagnetic radiation according to claim 1, wherein the method comprises the following steps: the concentration of the ethanol solution in the step (4) is 85-92%.
7. The method for preparing the lyocell fiber for preventing electromagnetic radiation according to claim 1, wherein the method comprises the following steps: the concentration of the bleaching agent solution in the step (5) is 0.1-0.3 g/L.
8. The method for preparing the lyocell fiber for preventing electromagnetic radiation according to claim 1, wherein the method comprises the following steps: the concentration of the oil bath solution in the step (7) is 3-4 g/L.
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