CN111118646A - Antibacterial moisture-absorbing temperature-adjusting elastic filament and preparation method and application thereof - Google Patents
Antibacterial moisture-absorbing temperature-adjusting elastic filament and preparation method and application thereof Download PDFInfo
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- CN111118646A CN111118646A CN201910476540.XA CN201910476540A CN111118646A CN 111118646 A CN111118646 A CN 111118646A CN 201910476540 A CN201910476540 A CN 201910476540A CN 111118646 A CN111118646 A CN 111118646A
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04B—KNITTING
- D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
- D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
- D04B1/16—Other fabrics or articles characterised primarily by the use of particular thread materials synthetic threads
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04B—KNITTING
- D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
- D04B21/14—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes
- D04B21/16—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes incorporating synthetic threads
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/061—Load-responsive characteristics elastic
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/13—Physical properties anti-allergenic or anti-bacterial
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Abstract
The invention relates to the field of high polymer materials and textile materials, in particular to an antibacterial moisture-absorbing temperature-regulating elastic filament, which is prepared by compounding pretreated chitosan with a functional modifier, then carrying out in-situ polymerization on the chitosan and nylon 66 salt to obtain a functional nylon compound slice, and finally carrying out a melt spinning process and a twisting process, wherein the filament number of the prepared functional elastic filament is 0.66-3.3dtex, the breaking strength is 4.0-6.5cN/dtex, the boiling water shrinkage rate is 3.5-7.5%, and the crimp shrinkage rate is 18-45%. The functional elastic filament prepared by the invention has multiple functions of antibiosis, moisture absorption, temperature regulation and the like, can be prepared into functional fabric for absorbing, transferring and discharging moisture of human bodies, has the antibacterial property of more than or equal to 80 percent, improves the humidity regulation capability by 30-80 percent and has the body sensing temperature variation of +/-1-3.0 ℃.
Description
Technical Field
The invention relates to the field of high polymer materials and textile materials, in particular to an antibacterial moisture-absorbing temperature-regulating elastic filament and a preparation method and application thereof.
Background
With the technological progress, people are not limited to the basic requirements of being full of warmness, and the requirements on the wearing comfort, the light warmth retention property, the air permeability, the antibacterial property and other functionalities of the clothes are increasingly common, particularly in the fields of leisure, sports and underwear, especially for people who move outdoors for a long time and soldiers who train in the field, the clothes cannot be frequently replaced and are long in time, bacteria are easy to breed, harm is caused to health, and the requirements on the clothes which are antibacterial, temperature-adjusting, moisture-permeable, dry and breathable are more urgent.
Currently, there are two main classes of antibacterial agents used in textiles, organic and inorganic. The organic antibacterial agent generally plays a role in inhibiting bacteria and resisting bacteria by attracting positive charge groups carried by active ingredients with negative charges on the surface of bacteria to destroy the cell membrane of the bacteria in a physical mode. The inorganic antibacterial agent causes the diffusion of trace metal ions gradually dissolved out from the fibers into bacterial cells, and causes bacterial metabolic disturbance to die.
The antibacterial fabric can be obtained by directly weaving antibacterial fibers into the antibacterial fabric or fixing the antibacterial agent on the fibers through post-treatment. Currently, in the antibacterial processing of textiles, the after-finishing method accounts for about 70%. The antibacterial fabric treated by the special antibacterial process has the characteristics of strong antibacterial pertinence, various antibacterial types and the like. The antibacterial after-finishing processing method is to finish the textile by using an antibacterial agent with certain washability, so that the antibacterial agent can be attached to the textile, and the existing fibers with antibacterial function, such as hemp fibers, chitin fibers, metal fibers and the like, are increasingly popular with people because the fibers have antibacterial property and lasting antibacterial property and do not need complicated subsequent processing treatment. The antibacterial agent mainly comprises amino cation and anions such as sialophospholipid constituting microbial cell wall, which attract each other to restrict the freedom of microbe and inhibit its metabolism and reproduction; or the low molecular weight chitosan molecule directly invades into the organism's cell, preventing the organism's genetic code from being copied from DNA to RNA, thus preventing the microorganism from breeding.
In addition, the earliest temperature-regulating textile is a fabric textile woven by adding a phase-change material (a substance with a melting point of 30-38 ℃ and a crystallization temperature of 10-30 ℃ is coated in a micron-sized polymer capsule) into viscose or acrylic (spun wool) fibers, and the heat absorption/heat release behavior of the textile when solid-liquid/liquid-solid phase change occurs is utilized to enable the periphery of a body to form a 'micro-circulation' environment similar to the 'air-conditioning' efficiency, so that the aim of effectively regulating the body temperature of a human body is fulfilled. But the material is limited by the spinning process in the fiber spinning process (the high temperature easily causes the capsules to break and lose the temperature adjusting performance, and the addition amount is limited), and the material has weak adjusting capability on the body temperature of a human body; in addition, other temperature-adjusting products in the market mostly adopt a mode of finishing the fabric, but the method uses more organic solvents, is not environment-friendly, and has obvious deficiency in temperature-adjusting durability.
From the viewpoint of human body's movement physiology, the thermoregulation of the human body is mainly achieved by discharging sweat or moisture out of the body without rest day and night. Especially, when the human body is in a hot or humid environment for a long time and can not discharge the moisture out of the human body in time, the temperature of the surface of the human body rises and perspiration appears, so that the 'microenvironment' moist heat under the clothes feels obvious, the human body feels obvious sultriness and uncomfortable, bacteria are easy to breed after a long time, and the health is certainly damaged! Especially for people engaged in field work for a long time, it is necessary to develop a garment which can resist bacteria, regulate temperature, absorb moisture and perspire.
Disclosure of Invention
In order to solve the problems that the existing fiber filament has single functionality and is limited by a spinning process in a fiber spinning process, the invention aims to provide an elastic filament which integrates the functions of antibiosis, moisture absorption and temperature regulation; a second object of the present invention is to propose a preparation method for synthesizing the elastic filament; the third purpose of the invention is to provide the application of the elastic filament in the preparation of the antibacterial moisture-absorbing temperature-adjusting functional fabric.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the antibacterial moisture-absorbing temperature-adjusting elastic filament is prepared by compounding chitosan and a functional modifier and then carrying out in-situ polymerization and spinning processes on the chitosan and nylon 66 salt, wherein the filament number is 0.66-3.3dtex, the breaking strength is 4.0-6.5cN/dtex, the boiling water shrinkage rate is 3.5-7.5%, and the crimp shrinkage rate is 18-45%.
When the 'microenvironment' of a human body generates damp heat, the functional modifier component in the filament fabric can adsorb the damp, and the damp is discharged out of the human body through the micropores of the fabric and the porous layer structure on the surface of the fiber; when the environmental temperature is low, the porous structure on the fiber surface in the filament fabric can absorb far infrared rays radiated by a human body, so that the aim of keeping warm is fulfilled; in addition, the fabric contains a chitosan component with natural antibacterial property, and the fabric has obvious antibacterial property. The product prepared by the method can meet the requirements of the current market on antibiosis, moisture absorption and temperature regulation, and overcomes the defects of other textile products in the current market on function singleness and durability.
Preferably, the modifier is pumice powder, and the particle size of the pumice powder is 5-50 mu m.
The large amount of dust or particles ejected during volcanic explosion, due to the ejection energy and pressure release during the explosion, has a large amount of porous structure on the surface of the pumice powder, and the porous structure has a size of more than 10m2The specific surface area is/g, so that if the fiber is added into the fiber, a porous layer can be formed on the surface of the fiber, moisture discharged by a body can be timely led out of the body when the ambient temperature is high, and when the ambient temperature is low, the porous structure on the surface of the fiber in the filament fabric can absorb far infrared rays radiated by a human body to achieve the aim ofThe purpose of keeping warm; in addition, the surface with porous structure can prevent hot air from leaking out, and the purpose of keeping warm can be achieved.
The preparation method of the antibacterial moisture-absorbing temperature-adjusting elastic filament is characterized by comprising the following steps of:
(1) pretreatment of chitosan: dissolving chitosan in a weakly acidic solvent, stirring to dissolve the chitosan uniformly, then adding a maleic anhydride acetone solution, continuing stirring, precipitating after the reaction is finished, filtering, drying and crushing for later use;
(2) pretreatment of a functional modifier: drying the active agent in a muffle furnace at the temperature of 300-550 ℃ for 5-8h, cooling, placing the cooled active agent in a glacial acetic acid solvent, adding the pretreated chitosan powder obtained in the step (1), heating to reflux, stirring for 8-12 h, filtering, washing, drying to obtain a functional modifier, and crushing;
(3) in-situ polymerization: polymerizing nylon 66 salt and the pretreated functional modifier obtained in the step (2) in situ to obtain functional nylon compound slices;
(4) spinning: and (4) carrying out vacuum drying treatment on the functional nylon compound slices obtained in the step (3), then carrying out melt extrusion through a screw, and carrying out steps of spinning box body-spinning assembly-slow cooling-oiling-bundling-winding-twisting and the like to obtain the elastic filament product with permanent antibacterial, moisture absorption and temperature regulation functions.
The chitosan has good effect of inhibiting the propagation of microorganisms, but the molecular structure of the chitosan contains more hydroxyl groups, so that the compatibility between the chitosan and organic high molecular polymers is poor. Therefore, if chitosan is added to the organic high molecular polymer, it is first modified to increase the compatibility with the organic high molecular polymer. According to the invention, maleic anhydride is used as a modifier, and a grafting reaction is carried out between an anhydride group in the maleic anhydride and a hydroxyl group on the surface of chitosan, so that a maleic acid group with high compatibility with an organic high molecular polymer is effectively grafted on the surface of the chitosan, and the compatibility is improved.
Meanwhile, as the surface of the pumice powder has a large number of porous structures, the pumice powder can easily adsorb water vapor and organic matters in the pumice powder, and the water in the pumice powder can be effectively removed and the organic matters can be decomposed at the same time through high-temperature hot baking. Then removing unstable substances through glacial acetic acid and taking the unstable substances as a catalyst to graft the pretreated chitosan onto the surface of the pumice powder, so that the unstable substances and the pumice powder are integrated.
The in-situ polymerization method is to disperse the nanoparticles in the monomers uniformly and then to initiate polymerization by using an initiator, so that the nanoparticles or molecules are dispersed on the polymer matrix uniformly and the in-situ molecular polymerization material is formed. The in-situ multiphase polymerization not only maintains the nanometer characteristic of the particles, but also realizes the uniform dispersion of the filling particles, and can form nanometer particles with elastic coating layers and core-shell structures. Because the outer layer is an organic polymer, it can increase the affinity of the material for the organic phase. The functional modifier and the monomer melt are directly mixed and then are subjected to polymerization modification under a polymerization process. Can promote the modifier to be well dispersed in a matrix, has obvious difference with the traditional melt blending or solution blending process, and also avoids the problem of functional modifier powder agglomeration caused by the traditional mixing process.
Preferably, the deacetylation degree of the chitosan in the step (1) is 55-95%, the particle size is 10-100 mu m, and the molecular weight is 1x104~1x106And the particle size after crushing is 5-50 mu m.
The solubility of chitosan in water is affected by the degree of deacetylation, and the higher the degree of deacetylation, the higher the solubility of chitosan in dilute aqueous acid, so that the reaction can be more complete.
Preferably, the mass ratio of chitosan to maleic anhydride in the step (1) is 1: (1-6).
Preferably, the mass ratio of the chitosan to the pumice powder in the step (2) is (0.1-1): 1; the pretreated functional modifier is crushed to a particle size of 0.02-0.8 mu m by a ball mill, and the specific surface area is 10-400 m2/g。
After the chitosan reacts with the pumice powder, the chitosan may agglomerate, if the chitosan is not ground, the chitosan may be dispersed unevenly in the in-situ polymerization process, which is not beneficial to the final forming of textile fibers, yarn breakage or defects on the surfaces of filaments are easy to occur in the spinning process, and the fiber performance is also reduced. The functional modifier is crushed to micro-nano level, so that the dispersion uniformity of the pretreated functional modifier in the in-situ polymerization process can be ensured, the yarn breakage or the surface defect of the filament can not occur in the spinning process, and the high-quality filament quality can also effectively ensure the realization of multiple functions such as antibiosis, moisture absorption, temperature regulation and the like.
Preferably, the addition amount of the functional modifier after the pretreatment in the step (3) is 0.05 to 2% of the weight of the nylon 66 salt.
According to the invention, the pretreated functional modifier is directly added into the nylon 66 salt for in-situ polymerization, and compared with the traditional melt blending or solution blending process, the method has a better and more obvious dispersion effect of the functional modifier, and avoids the problem of functional modifier powder agglomeration caused by the traditional mixing process.
Preferably, the temperature control in the in-situ polymerization process in the step (3) is divided into three stages: the temperature of the material is controlled to be 210-215 ℃ before the material enters the first high-pressure pipe; the material is maintained at 235-270 ℃ in the process that the higher pipe enters the transverse pipe; after the materials enter the second high pipe, controlling the temperature to be 260-275 ℃ so as to keep the polycondensation temperature to be 265-275 ℃; then, the materials sequentially pass through a decompression pump, a flash evaporator and a deaerator, and the temperature is controlled to be 270-290 ℃; the polymerization pressure is 10 to 20kg/cm2And the pressure maintaining time is 1-3 hours.
Preferably, in the twisting step in the step (4), the D/Y ratio is 1.2-1.5; the friction disc is made of ceramic and has an assembly form of 1-5-3; the temperature of the hot roller is 190-235 ℃, and the drafting multiple is 1.25-1.75; the processing speed is 400-800 m/min. A
The functional fabric prepared from the antibacterial moisture-absorbing temperature-regulating elastic filament has the antibacterial property of more than or equal to 80%, the humidity-regulating capacity is improved by 30-80%, and the body sensing temperature changes by +/-1-3 ℃.
Therefore, compared with the prior art, the invention has the following beneficial effects:
(1) the prepared functional elastic filament has multiple functions of antibiosis, moisture absorption, temperature regulation and the like;
(2) according to the invention, through in-situ polymerization, the functional modifier in the fiber has excellent compatibility with nylon, and can be effectively dispersed to prevent agglomeration, so that the performance of the fiber is more stable;
(3) can be made into a fabric which has the antibacterial function and can absorb, transfer and discharge the moisture of the human body.
Detailed Description
The present invention will be described in more detail with reference to examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention. In the present invention, all the equipment, materials and the like are commercially available or commonly used in the industry, if not specified. The methods in the following examples are conventional in the art unless otherwise specified.
The main raw materials are as follows:
nylon 66 salt: nylon chemical company, magic horse; modifying agent: is sold on the market; and (3) chitosan: it is commercially available.
Example 1
The deacetylation degree is 60%, the particle size is 50-80 μm, and the molecular weight is 5x105Dissolving the chitosan in a weakly acidic solvent, stirring to uniformly dissolve the chitosan, and then adding a maleic anhydride acetone solution to ensure that the mass ratio of the chitosan to the maleic anhydride is 1: 1, continuously stirring, precipitating after the reaction is finished, filtering, drying and crushing for later use. The particle size after crushing is 20-50 mu m.
And firing 50g of pumice powder with the particle size of 20-50 mu m for 5.0h at 550 ℃ in a muffle furnace, placing the pumice powder in 200ml of glacial acetic acid solvent after cooling, adding 50g of the pretreated chitosan, heating and refluxing for 12h, filtering, washing and drying to obtain a functional modifier, and crushing the functional modifier into 0.4-0.8 mu m powder by using a ball mill for later use.
Weighing 50g of the treated functional modifier and 25kg of nylon 66 salt, stirring, mixing and dispersing uniformly in a storage barrel, and performing specific chain shrinkageThe polymerization process (i.e. polymerization + post-polycondensation reaction, i.e. horizontal tubular continuous polycondensation process) maintains the concentration of the nylon 66 salt aqueous solution at about 60%. The materials are continuously sent into a preheater through a plunger pump, enter a first high pipe after being preheated to 215 ℃, and are continuously pushed into a first transverse pipe and a second transverse pipe, the first high pipe keeps the materials at 245 ℃ in the process of entering a transverse pipe, then the materials are pushed into the second high pipe, the temperature of the materials is controlled between 260 ℃ and 270 ℃ after the materials enter the second high pipe, and a large amount of water vapor in the materials is evaporated and discharged through an exhaust pipe; the nylon 66 salt concentration increased and polycondensation was initiated (temperature was maintained at 260 ℃.); the polymer melt passes through a decompression pump and then enters a flash evaporator and a deaerator (the temperature is maintained at 270 ℃ C. and 275 ℃ C.), wherein the polymerization pressure is 10kg/cm2The dwell time was 1 hour. And after removing residual water, feeding the polymer melt into a post-polycondensation kettle for further polymerization, wherein the polymerization time is about 30min, extruding a product by a discharge screw, granulating by a casting belt, and drying in vacuum at the drying temperature of 90 ℃ for 48 hours to obtain the functional nylon 66 composite slice.
After the obtained functional nylon 66 composite slice is subjected to dynamic vacuum drying for 8 hours at 100 ℃, the slice is extruded by a screw extruder and then is sent to a spinning machine, a melt is quantitatively pressed into a spinning part by a metering pump, the filtration precision of a spinning pack is reduced by 10%, and the nylon 66 melt is extruded in a filament state through a spinning hole on a spinneret plate, wherein the aperture of the spinneret plate is 0.4mm, and the length-diameter ratio is 2.0; cooling by circular air blowing, bundling and oiling by an oil nozzle, and winding to obtain the POY filaments at a winding speed of 3800 m/min. Then twisting and drafting to obtain the functional elastic filament. Wherein the hot roll temperature is 230 ℃, the D/Y ratio is 1.25, the draft ratio is 1.35, and the winding speed is 800 m/min.
Tests show that the strength of the obtained multifunctional nylon 66 filament with the filament number of 3.0 dtex reaches 6.5cN/dtex, the boiling water shrinkage rate is 4.5 percent, and the crimp shrinkage rate is 25 percent.
Tests show that the antibacterial property of the knitted functional fabric woven based on the filament reaches 83%, the humidity-adjusting capacity is improved by 30%, and the somatosensory temperature changes by +/-1 ℃.
Example 2
The deacetylation degree is 80%, the particle size is 20-50 μm, and the molecular weight is 8x105Dissolving the chitosan in a weakly acidic solvent, stirring to uniformly dissolve the chitosan, and then adding a maleic anhydride acetone solution to ensure that the mass ratio of the chitosan to the maleic anhydride is 1: 2, continuing stirring, precipitating after the reaction is finished, filtering, drying and crushing for later use. The particle size after crushing is 10-30 mu m.
Then firing 100g of pumice powder with the particle size of 10-30 mu m for 6.0h at 450 ℃ in a muffle furnace, placing the pumice powder in 400ml of glacial acetic acid solvent after cooling, adding 50g of the pretreated chitosan, heating and refluxing for 10h, filtering, washing and drying to obtain a functional modifier, and crushing the functional modifier into 0.2-0.5 mu m powder by a ball mill for later use.
150g of the treated functional modifier and 20kg of nylon 66 salt are weighed in a storage barrel, stirred, mixed and dispersed uniformly, and then subjected to a specific chain polycondensation process (namely polymerization and post-polycondensation reaction, namely a horizontal tube type continuous polycondensation process) to maintain the concentration of the aqueous solution of the nylon 66 salt at about 60%. The materials are continuously sent into a preheater through a plunger pump, enter a first high pipe after being preheated to 210 ℃, and are continuously pushed into a first transverse pipe and a second transverse pipe, the first high pipe keeps the materials at 245 ℃ in the process of entering a transverse pipe, then the materials are pushed into the second high pipe, the temperature of the materials is controlled between 260 ℃ and 275 ℃ after the materials enter the second high pipe, and a large amount of water vapor in the materials is evaporated and discharged through an exhaust pipe; the nylon 66 salt concentration increased and polycondensation was initiated (temperature was maintained at 270 ℃ C.); the polymer melt passes through a decompression pump and then enters a flash evaporator and a deaerator (the temperature is maintained at 280 ℃ C. and 285 ℃ C.), wherein the polymerization pressure is 20kg/cm2The dwell time was 3 hours. And after removing residual water, feeding the polymer melt into a post-polycondensation kettle for further polymerization, wherein the polymerization time is about 90min, extruding a product by a discharge screw, granulating by a casting belt, and drying in vacuum at the drying temperature of 90 ℃ for 48 hours to obtain the functional nylon 66 composite slice.
After the obtained functional nylon 66 composite slice is subjected to dynamic vacuum drying for 8 hours at 100 ℃, the slice is extruded by a screw extruder and then is sent to a spinning machine, a melt is quantitatively pressed into a spinning part by a metering pump, the filtration precision of a spinning pack is reduced by 10%, and the nylon 66 melt is extruded in a filament state through a spinning hole on a spinneret plate, wherein the aperture of the spinneret plate is 0.3 mm, and the length-diameter ratio is 2.5; cooling by circular blowing, bundling and oiling by an oil nozzle, and winding to obtain POY filaments with the winding speed of 3200 m/min. Then twisting and drafting to obtain the functional elastic filament. Wherein the hot roll temperature is 225 ℃, the D/Y ratio is 1.35, the draft ratio is 1.45, and the winding speed is 600 m/min.
Tests show that the strength of the obtained multifunctional nylon 66 filament with the filament number of 1.65dtex reaches 6.0cN/dtex, the boiling water shrinkage rate is 4.0 percent, and the crimp shrinkage rate is 35 percent.
Tests show that the antibacterial property of the knitted functional fabric woven based on the filament reaches 86%, the humidity-adjusting capacity is improved by 45%, and the body-sensing temperature changes by +/-1.5 ℃.
Example 3
The deacetylation degree is 80%, the particle size is 20-50 μm, and the molecular weight is 2x104Dissolving the chitosan in a weakly acidic solvent, stirring to uniformly dissolve the chitosan, and then adding a maleic anhydride acetone solution to ensure that the mass ratio of the chitosan to the maleic anhydride is 1: and 5, continuously stirring, precipitating after the reaction is finished, filtering, drying and crushing for later use. The particle size after crushing is 5-15 mu m.
Then burning 200g of pumice powder with the particle size of 5-15 mu m for 8.0h at 350 ℃ in a muffle furnace, placing the pumice powder in 800ml of glacial acetic acid solvent after cooling, adding 50g of the pretreated chitosan, heating and refluxing for 10h, filtering, washing and drying to obtain a functional modifier, and crushing the functional modifier into 0.02-0.1 mu m powder by a ball mill for later use.
250g of the treated functional modifier and 10kg of nylon 66 salt are weighed in a storage barrel, stirred, mixed and dispersed uniformly, and then subjected to a specific chain polycondensation process (namely polymerization and post-polycondensation reaction, namely a horizontal tube type continuous polycondensation process) to maintain the concentration of the aqueous solution of the nylon 66 salt at about 60%. Continuously feeding the above materials into a preheater via a plunger pump, preheating to 225 deg.C, feeding into a first pipe, continuously pushing into a first transverse pipe and a second transverse pipe, and maintaining the materials at 255 deg.C in the process of feeding into the transverse pipeThe material is pushed into the second high pipe at the temperature of 270 ℃ and 285 ℃, and a large amount of water vapor in the material is evaporated and discharged through the exhaust pipe; the nylon 66 salt concentration increased and polycondensation started (temperature maintained at 265 ℃. 275 ℃); the polymer melt enters a flash evaporator and a deaerator in sequence through a decompression pump (the temperature is maintained at 285 ℃ C. and 290 ℃ C.), wherein the polymerization pressure is 12kg/cm2The dwell time was 1.5 hours. And after removing residual water, feeding the polymer melt into a post-polycondensation kettle for further polymerization, wherein the polymerization time is about 45min, extruding a product by a discharge screw, granulating by a casting belt, and drying in vacuum at 96 ℃ for 20 hours to obtain the functional nylon 66 composite slice.
After the obtained functional nylon 66 composite slice is subjected to dynamic vacuum drying for 8 hours at 100 ℃, the slice is extruded by a screw extruder and then is sent to a spinning machine, a melt is quantitatively pressed into a spinning part by a metering pump, the filtration precision of a spinning pack is reduced by 10%, and the nylon 66 melt is extruded in a filament state through a spinning hole on a spinneret plate, wherein the aperture of the spinneret plate is 0.2 mm, and the length-diameter ratio is 3.5; cooling by circular air blowing, bundling and oiling by an oil nozzle, and winding to obtain POY filaments at the winding speed of 3300 m/min. Then twisting and drafting to obtain the functional elastic filament. Wherein the hot roll temperature is 220 ℃, the D/Y ratio is 1.40, the draft ratio is 1.30, and the winding speed is 400 m/min.
Through tests, the strength of the obtained multifunctional nylon 66 filament with the filament number of 0.88dtex reaches 5.3cN/dtex, the boiling water shrinkage rate is 6.0 percent, and the crimp shrinkage rate is 38 percent.
Tests show that the antibacterial property of the knitted functional fabric woven based on the filament reaches 90%, the humidity-adjusting capacity is improved by 65%, and the body-sensing temperature changes by +/-2.5 ℃.
Example 4
The deacetylation degree is 80%, the particle size is 20-50 μm, and the molecular weight is 8x105Dissolving the chitosan in a weakly acidic solvent, stirring to uniformly dissolve the chitosan, and then adding a maleic anhydride acetone solution to ensure that the mass ratio of the chitosan to the maleic anhydride is 1: 6, continuously stirring, precipitating after the reaction is finished, filtering, drying,Pulverizing for use. The particle size after crushing is 10-30 mu m.
Then firing 100g of pumice powder with the particle size of 30-50 mu m for 6.0h at 450 ℃ in a muffle furnace, placing the pumice powder in 400ml of glacial acetic acid solvent after cooling, adding 20g of the pretreated chitosan, heating and refluxing for 10h, filtering, washing and drying to obtain a functional modifier, and crushing the functional modifier into 0.2-0.5 mu m powder by a ball mill for later use.
100g of the treated functional modifier and 20kg of nylon 66 salt are weighed in a storage barrel, stirred, mixed and dispersed uniformly, and then subjected to a specific chain polycondensation process (namely polymerization and post-polycondensation reaction, namely a horizontal tube type continuous polycondensation process) to maintain the concentration of the aqueous solution of the nylon 66 salt at about 60%. The materials are continuously sent into a preheater through a plunger pump, enter a first high pipe after being preheated to 210 ℃, and are continuously pushed into a first transverse pipe and a second transverse pipe, the first high pipe keeps the materials at 245 ℃ in the process of entering a transverse pipe, then the materials are pushed into the second high pipe, the temperature of the materials is controlled between 260 ℃ and 275 ℃ after the materials enter the second high pipe, and a large amount of water vapor in the materials is evaporated and discharged through an exhaust pipe; the nylon 66 salt concentration increased and polycondensation was initiated (temperature was maintained at 270 ℃ C.); the polymer melt passes through a decompression pump and then enters a flash evaporator and a deaerator (the temperature is maintained at 280 ℃ C. and 285 ℃ C.), wherein the polymerization pressure is 20kg/cm2The dwell time was 3 hours. And after removing residual water, feeding the polymer melt into a post-polycondensation kettle for further polymerization, wherein the polymerization time is about 90min, extruding a product by a discharge screw, granulating by a casting belt, and drying in vacuum at the drying temperature of 90 ℃ for 48 hours to obtain the functional nylon 66 composite slice.
After the obtained functional nylon 66 composite slice is subjected to dynamic vacuum drying for 8 hours at 100 ℃, the slice is extruded by a screw extruder and then is sent to a spinning machine, a melt is quantitatively pressed into a spinning part by a metering pump, the filtration precision of a spinning pack is reduced by 10%, and the nylon 66 melt is extruded in a filament state through a spinning hole on a spinneret plate, wherein the aperture of the spinneret plate is 0.3 mm, and the length-diameter ratio is 2.5; cooling by circular blowing, bundling and oiling by an oil nozzle, and winding to obtain POY filaments with the winding speed of 3200 m/min. Then twisting and drafting to obtain the functional elastic filament. Wherein the hot roll temperature is 225 ℃, the D/Y ratio is 1.25, the draft ratio is 1.35, and the winding speed is 600 m/min.
Tests show that the strength of the obtained multifunctional nylon 66 filament with the filament number of 0.66dtex reaches 5.5cN/dtex, the boiling water shrinkage rate is 3.5 percent, and the crimp shrinkage rate is 20 percent.
Tests show that the antibacterial property of the knitted functional fabric woven based on the filament reaches 80%, the humidity-adjusting capacity is improved by 38%, and the somatosensory temperature changes by +/-1.3 ℃.
Example 5
The deacetylation degree is 95%, the particle size is 10-25 μm, and the molecular weight is 1x106Dissolving the chitosan in a weakly acidic solvent, stirring to uniformly dissolve the chitosan, and then adding a maleic anhydride acetone solution to ensure that the mass ratio of the chitosan to the maleic anhydride is 1: and 4, continuing stirring, precipitating after the reaction is finished, filtering, drying and crushing for later use. The particle size after crushing is 10-30 mu m.
Then burning 200g of pumice powder with the particle size of 10-30 mu m for 6.0h at 450 ℃ in a muffle furnace, placing the pumice powder in 400ml of glacial acetic acid solvent after cooling, adding 200g of the pretreated chitosan, heating and refluxing for 10h, filtering, washing and drying to obtain a functional modifier, and crushing the functional modifier into 0.2-0.5 mu m powder by a ball mill for later use.
400g of the treated functional modifier and 20kg of nylon 66 salt are weighed in a storage barrel, stirred, mixed and dispersed uniformly, and then subjected to a specific chain polycondensation process (namely polymerization and post-polycondensation reaction, namely a horizontal tube type continuous polycondensation process) to maintain the concentration of the aqueous solution of the nylon 66 salt at about 60%. The materials are continuously sent into a preheater through a plunger pump, enter a first high pipe after being preheated to 210 ℃, and are continuously pushed into a first transverse pipe and a second transverse pipe, the first high pipe keeps the materials at 245 ℃ in the process of entering a transverse pipe, then the materials are pushed into the second high pipe, the temperature of the materials is controlled between 260 ℃ and 275 ℃ after the materials enter the second high pipe, and a large amount of water vapor in the materials is evaporated and discharged through an exhaust pipe; the nylon 66 salt concentration increased and polycondensation was initiated (temperature was maintained at 270 ℃ C.); the polymer melt enters a flash evaporator and a deaerator sequentially through a decompression pump (the temperature is maintained at 280 ℃ and 285℃)) Wherein the polymerization pressure is 20kg/cm2The dwell time was 3 hours. And after removing residual water, feeding the polymer melt into a post-polycondensation kettle for further polymerization, wherein the polymerization time is about 90min, extruding a product by a discharge screw, granulating by a casting belt, and drying in vacuum at the drying temperature of 90 ℃ for 48 hours to obtain the functional nylon 66 composite slice.
After the obtained functional nylon 66 composite slice is subjected to dynamic vacuum drying for 8 hours at 100 ℃, the slice is extruded by a screw extruder and then is sent to a spinning machine, a melt is quantitatively pressed into a spinning part by a metering pump, the filtration precision of a spinning pack is reduced by 10%, and the nylon 66 melt is extruded in a filament state through a spinning hole on a spinneret plate, wherein the aperture of the spinneret plate is 0.3 mm, and the length-diameter ratio is 2.5; cooling by circular air blowing, bundling and oiling by an oil nozzle, and winding to obtain the POY filaments, wherein the winding speed is 4000 m/min. Then twisting and drafting to obtain the functional elastic filament. Wherein the hot roll temperature is 225 ℃, the D/Y ratio is 1.25, the draft ratio is 1.25, and the winding speed is 600 m/min.
Tests show that the strength of the obtained multifunctional nylon 66 filament with the filament number of 1.65dtex reaches 5.4cN/dtex, the boiling water shrinkage rate is 5.5 percent, and the crimp shrinkage rate is 22 percent.
Tests show that the antibacterial property of the knitted functional fabric woven based on the filament reaches 95%, the humidity-adjusting capacity is improved by 55%, and the body-sensing temperature changes by +/-2.2 ℃.
The above-described preferred embodiments are merely illustrative and explanatory of the present invention and are not restrictive of the invention as claimed. Although the present invention has been described in detail by the inventor, it is obvious that various modifications and/or additions can be made to the described embodiments or replacements can be made by those skilled in the art according to the disclosure of the summary of the invention and the embodiments, and the technical effects of the present invention can be achieved, therefore, the detailed description is omitted. The terms appearing in the present invention are used for illustration and understanding of the technical aspects of the present invention, and do not constitute limitations of the present invention.
Claims (10)
1. The antibacterial moisture-absorbing temperature-adjusting elastic filament is characterized in that the elastic filament is prepared by compounding chitosan and a functional modifier and then carrying out in-situ polymerization, spinning and twisting processes on the chitosan and nylon 66 salt, wherein the filament number is 0.66-3.3dtex, the breaking strength is 4.0-6.5cN/dtex, the boiling water shrinkage rate is 3.5-7.5%, and the crimp shrinkage rate is 18-45%.
2. The antibacterial moisture-absorbing temperature-regulating elastic filament according to claim 1, wherein the modifier is pumice powder with the particle size of 5-50 μm.
3. A process for preparing an antibacterial, hygroscopic, thermoregulating elastic filament according to claim 1 or 2, characterized in that it comprises the steps of:
(1) pretreatment of chitosan: dissolving chitosan in a weakly acidic solvent, stirring to dissolve the chitosan uniformly, then adding a maleic anhydride acetone solution, continuing stirring, precipitating after the reaction is finished, filtering, drying and crushing for later use;
(2) pretreatment of a functional modifier: drying the active agent in a muffle furnace at 300-550 ℃ for 5-8h, cooling, placing in a glacial acetic acid solvent, adding the pretreated chitosan powder obtained in the step (1), heating to reflux, stirring for 8-12 h, filtering, washing, drying and crushing;
(3) in-situ polymerization: polymerizing nylon 66 salt and the pretreated functional modifier obtained in the step (2) in situ to obtain functional nylon compound slices;
(4) spinning: and (4) carrying out vacuum drying treatment on the functional nylon compound slices obtained in the step (3), then carrying out melt extrusion through a screw, and carrying out steps of spinning box body-spinning assembly-slow cooling-oiling-bundling-winding-twisting and the like to obtain the elastic filament product with permanent antibacterial, moisture absorption and temperature regulation functions.
4. The preparation method of the antibacterial moisture-absorbing temperature-regulating elastic filament yarn according to claim 3, wherein the deacetylation degree of chitosan in the step (1) is 55-95%, and the particle size is 10-100 mu mm, molecular weight 1x104~1x106And the particle size after crushing is 5-50 mu m.
5. The method for preparing an antibacterial moisture-absorbing temperature-regulating elastic filament according to claim 3 or 4, wherein the mass ratio of the chitosan to the maleic anhydride in the step (1) is 1: (1-6).
6. The preparation method of the antibacterial moisture-absorbing temperature-regulating elastic filament yarn according to claim 3, wherein the mass ratio of the chitosan to the pumice powder in the step (2) is (0.1-1): 1; the pretreated functional modifier is crushed to a particle size of 0.02-0.8 mu m by a ball mill, and the specific surface area is 10-400 m2/g。
7. The method for preparing the antibacterial moisture-absorbing temperature-regulating elastic filament yarn as claimed in claim 3, wherein the addition amount of the functional modifier after pretreatment in the step (3) is 0.05-2% of the weight of nylon 66 salt.
8. The method for preparing an antibacterial moisture-absorbing temperature-regulating elastic filament according to claim 3 or 6, wherein the temperature control in the in-situ polymerization process in the step (3) is divided into three stages: the temperature of the material is controlled to be 210-215 ℃ before the material enters the first high-pressure pipe; the material is maintained at 235-270 ℃ in the process that the higher pipe enters the transverse pipe; after the materials enter the second high pipe, controlling the temperature to be 260-275 ℃ so as to keep the polycondensation temperature to be 265-275 ℃; then, the materials sequentially pass through a decompression pump, a flash evaporator and a deaerator, and the temperature is controlled to be 270-290 ℃; the polymerization pressure is 10 to 20kg/cm2And the pressure maintaining time is 1-3 hours.
9. The method for preparing the antibacterial moisture-absorbing temperature-regulating elastic filament yarn according to claim 3, wherein in the twisting step in the step (4), the D/Y ratio is 1.2-1.5; the friction disc is made of ceramic and has an assembly form of 1-5-3; the temperature of the hot roller is 190-235 ℃, and the drafting multiple is 1.25-1.75; the processing speed is 400-800 m/min.
10. The functional fabric prepared from the antibacterial moisture-absorbing temperature-adjusting elastic filament yarn as claimed in claim 1 or 2 is characterized in that the antibacterial property of the fabric is greater than or equal to 80%, the humidity-adjusting capacity is improved by 30-80%, and the sensible temperature changes by +/-1-3 ℃.
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