CN111485328A - Preparation method and device of flame-retardant nanofiber composite material - Google Patents
Preparation method and device of flame-retardant nanofiber composite material Download PDFInfo
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- CN111485328A CN111485328A CN202010191236.3A CN202010191236A CN111485328A CN 111485328 A CN111485328 A CN 111485328A CN 202010191236 A CN202010191236 A CN 202010191236A CN 111485328 A CN111485328 A CN 111485328A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
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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
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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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
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
- D01D5/0084—Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses
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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
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
- D01F6/12—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polymers of fluorinated hydrocarbons
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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
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/43—Acrylonitrile series
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/007—Addition polymers
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
- D06C7/02—Setting
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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
- D10B2505/00—Industrial
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- Chemical Kinetics & Catalysis (AREA)
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- Mechanical Engineering (AREA)
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- Polymers & Plastics (AREA)
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Abstract
The invention relates to the technical field of textile processing, and provides a preparation method of a flame-retardant nanofiber composite material aiming at the problem of more smoke when flame-retardant fibers are subjected to flame retardance, which comprises the following steps: preparing polyacrylonitrile into spinning solution, spraying out nano-fibers through a spinning machine, depositing the nano-fibers on textile fibers, performing hot-pressing and shaping, performing pre-oxidation treatment to perform secondary hot-pressing and shaping, and finally winding and collecting. The invention adopts the electrostatic spinning technology, combines common textile fibers and nano fibers, and leads the composite material to have flame retardance and flame resistance through hot press sizing and pre-oxidation treatment, and the nano fibers prepared by the electrostatic spinning method have the advantages of thin diameter, large specific surface area, high porosity, excellent filtering performance and strong adsorption capacity to smoke and harmful gases while being flame retardant. The invention also provides a device for the preparation method.
Description
Technical Field
The invention relates to the technical field of textile processing, in particular to a preparation method and a device of a flame-retardant nanofiber composite material.
Background
In recent years, with the rapid development of science and technology, people develop more and more new materials in the field of polymer materials, and face a great problem of how to improve the flame retardance and smoke suppression technology of the polymer materials while enjoying the convenience brought by the new materials. In daily life, textiles such as clothes, curtains, sofas and the like are easy to ignite to cause fire, and most of the textiles are composed of synthetic fibers such as polyester fibers (terylene), polyamide fibers (nylon), polyacrylonitrile fibers (acrylic fibers) and viscose fibers through single spinning or blended spinning. Common flame retardants include chemical flame retardants and filler type flame retardants, and flame retardant properties can be imparted to the fibers by adding the flame retardants. For example, a patent with publication number CN108977915A and name 'a flame-retardant polypropylene staple fiber and a preparation method thereof', discloses a flame-retardant polypropylene staple fiber, which is prepared from 80-120 parts by weight of polypropylene slices, 40-60 parts by weight of polyacrylonitrile-based carbon fibers, 40-60 parts by weight of flame retardant, 20-40 parts by weight of dispersant, 10-20 parts by weight of plasticizer and 20-30 parts by weight of color master batch. However, the flame retardant such as antimony oxide used in the method generates much smoke and harmful gas when the flame retardant is used, and causes direct harm to the life safety and living environment of people. Accordingly, there is a need for a flame retardant fiber that is desirable.
Polyacrylonitrile fiber is a common synthetic fiber, and has a soft hand feeling of wool when used as a civil textile. In addition, the carbon fiber can be used as a raw material for producing carbon fibers, and a high-performance carbon fiber material is prepared by pre-oxidation and carbonization treatment. In the pre-oxidation process, the polyacrylonitrile fiber can be subjected to cyclization, oxidation, dehydrogenation, crosslinking and other reactions, and a linear molecular chain is converted into a trapezoidal structure, so that the polyacrylonitrile fiber has the characteristics of high temperature resistance, flame retardance and flame resistance.
The electrospinning technique is a spinning technique in which a polymer solution is formed into nanofibers by applying a high voltage electric field between a polymer solution injector and a receiver. The nano-fiber prepared by the electrostatic spinning method has smaller diameter and larger specific surface area, so that the fiber has various unique properties and has great application potential in the fields of biomedicine, air filtration, protective clothing and the like. The electrostatic spinning nanofiber needs a receiver during preparation, the randomly deposited nanofiber is usually collected by using non-woven fabrics, and when the single nanofiber is used, the strength is low, the application range is limited, and the advantages of the nanofiber material characteristics and the high specific surface area cannot be embodied.
Disclosure of Invention
The invention aims to overcome the problem that a large amount of smoke is generated during flame retardance of the conventional flame-retardant fiber, and provides a preparation method of a flame-retardant nanofiber composite material. The nano composite fiber material has the characteristics of low price, green and environment-friendly preparation method, safety, controllability and suitability for large-scale production, and has the advantages of high specific surface area, high porosity and excellent filtering performance, flame retardance and strong adsorption capacity to smoke and harmful gases. The invention also provides a device for the preparation method.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the flame-retardant nanofiber composite material is characterized by comprising the following steps of:
(1) preparing a spinning solution: dissolving polyacrylonitrile in N, N-dimethylformamide to prepare polyacrylonitrile spinning solution with the mass fraction of 8% -20%;
(2) electrostatic spinning: adjusting the spinning voltage of an electrostatic spinning machine to be 20-50 kV, spraying the spinning solution to form nano fibers with the diameter of 50-1000 nm, spraying the nano fibers onto a base material, wherein the base material is textile fibers, and the receiving distance of the base material is 10-20 cm;
(3) hot-pressing and shaping: conveying the base material sprayed with the nano fibers into a hot press, controlling the hot pressing temperature at 60-100 ℃, the hot pressing time at 1-5 min, and the hot pressing pressure at 1-100 MPa;
(4) pre-oxidation treatment: sending the hot-pressed and shaped material into a heat box, and carrying out low-temperature pre-oxidation in inert gas for 10-20 min, wherein the temperature is set between 200 ℃ and 240 ℃;
(5) winding to form a material: and (4) carrying out the hot-press forming on the composite material subjected to the pre-oxidation treatment again, and finally winding and collecting.
The invention prepares polyacrylonitrile into nano-fiber through electrostatic spinning, and the nano-fiber is sprayed on the surface of a base material, and in the electrostatic spinning process, a solvent is volatilized rapidly, and the nano-fiber is adhered on the surface of the base material under the action of electric field force and electrostatic force. In order to enhance the bonding force between the nanofiber layer and the base material layer, hot pressing treatment is required, on one hand, surface finishing is performed on the fluffy nanofibers, and on the other hand, the nanofibers are attached to the base material more tightly. The composite material of the invention is not limited to two layers of materials, but can also be a composite material of three or more layers, and the nano fiber can be used as a surface layer, a bottom layer or a middle layer. And after hot-pressing and shaping, performing preoxidation process treatment to enable the polyacrylonitrile fiber to undergo cyclization, oxidation, dehydrogenation, crosslinking and other reactions, so that a linear molecular chain is converted into a trapezoidal structure, thereby having the characteristics of high temperature resistance, flame retardance and flame resistance. Polyacrylonitrile fibers, when thermally cracked, emit combustible gases such as carbon monoxide, acetonitrile, acrylonitrile, vinyl acetonitrile, various unsaturated hydrocarbons and chain scission products. The cross-linking of linear macromolecules is one of the methods for achieving flame retardance, and after the pre-oxidation process treatment, the cross-linking effect can limit cracking to generate combustible gas, so that the purpose of gas-phase flame retardance is achieved. In the current technical route, the thermal oxidation stabilization of the polyacrylonitrile fiber is generally performed in an air atmosphere, taking the preparation of the carbon fiber and the adsorbing material from the polyacrylonitrile fiber as an example, under the current technical conditions, the thermal oxidation stabilization time of the polyacrylonitrile fiber is usually 30-90 min, and accounts for more than 80-90% of the time consumed in the whole preparation process. The polyacrylonitrile nano fiber has the advantages that the average diameter of the fiber is in the nanometer level, so that the preoxidation time is shorter than that of the traditional micron-sized polyacrylonitrile fiber, the cyclization reaction and oxidation reaction are faster, and a large amount of time is saved. In order to prevent the base material from decomposing at high temperature, a low-temperature pre-oxidation mode in inert gas is adopted.
The invention adopts the electrostatic spinning technology, combines common textile fibers and nano fibers, realizes the continuous and rapid preparation of the flame-retardant nano fiber composite material through hot press shaping and pre-oxidation treatment, has low price, green and environment-friendly preparation method, safety and controllability, and is suitable for large-scale production. The polyacrylonitrile nanometer pre-oxidized fiber makes the composite material possess fire retarding performance. The nano-fiber prepared by the electrostatic spinning method has the advantages of small diameter, large specific surface area, high porosity and internal randomly crossed network structure, so that the nano-fiber has excellent filtering performance and strong adsorption capacity to smoke and harmful gases while being flame-retardant.
Preferably, in the step (1), polyacrylonitrile and N, N-dimethylformamide are mixed and then are continuously stirred for 20-24 hours in a water bath at the temperature of 40-60 ℃.
Preferably, the polyacrylonitrile in the step (1) is subjected to modification treatment, and the method comprises the following steps:
1) mixing polyacrylonitrile, sodium hydroxide and water according to a mass ratio of (1-3) to (6) (40-60), performing reflux reaction for 22-24 h, adjusting the reaction liquid to be neutral, precipitating with methanol, washing and drying to obtain a product a;
2) mixing the product a, glycerol and N, N-dimethylformamide according to the mass ratio of 50 (9-15) to (50-80), and reacting at the temperature of 100 ℃ and 120 ℃ for 8-12 h to obtain a product b;
3) and mixing the product b, a double-spiro phosphonate flame retardant and water according to the mass ratio of 1 (2-4) to (2-6), and reacting at 90 ℃ to obtain the modified polyacrylonitrile, wherein the double-spiro phosphonate flame retardant is 2,4,8, 10-tetraoxy-3, 9-diphosphospiro [5,5] undecane-3, 9-dioxo-3, 9-dipropionic acid.
In order to further increase the flame retardancy of the composite fiber, polyacrylonitrile is subjected to modification treatment. Double spiro phosphineThe acid ester flame retardant is a cage-shaped compound with highly symmetrical structure, integrates an acid source and a carbon source, can well dehydrate to form carbon in the combustion process and plays a role in flame retardance. The double-spiro phosphonate flame retardant is directly added into the spinning solution, polyacrylonitrile cannot react with the double-spiro phosphonate flame retardant, and the polyacrylonitrile is poor in adhesion with fibers after spinning and is easy to separate out and fall off. 2,4,8, 10-tetraoxy-3, 9-diphosphospiro [5,5]]Undecane-3, 9-dioxo-3, 9-dipropionic acid is one of the industrially produced double-spiro flame retardants, which contains two symmetrical carboxyl groups. In order to enable the double-spiro phosphonate flame retardant to be combined with polyacrylonitrile through a chemical bond, a cyano group of the polyacrylonitrile is firstly converted into an easily-reacted carboxyl group, and specifically, the cyano group is firstly converted into sodium carboxylate by adding strong base, and then is neutralized into the carboxyl group by using acid. OH in alkali solution when polyacrylonitrile reacts with alkali-Nucleophilic attack on carbon atom of cyano group to make nitrogen atom of cyano group and carbon atom of adjacent cyano group connected to form six-membered ring at OH-The six-membered ring is hydrolyzed to generate sodium carboxylate groups. The ratio of sodium hydroxide to polyacrylonitrile needs to be controlled in the step, the invention optimizes the mass ratio of the polyacrylonitrile to the sodium hydroxide to the water by experiments to be (1-3):6 (40-60), the concentration of the sodium hydroxide is higher, the mole number of the sodium hydroxide is far lower than that of cyano-group in the polyacrylonitrile, the six-membered ring is partially hydrolyzed, and finally about 10% of the cyano-group is converted into carboxyl group by measurement, so that the main structure of the polyacrylonitrile is not changed greatly. The existence of non-hydrolyzed six-membered ring is helpful for flame retardance, so that the heat released by the cyclization of cyano group is greatly reduced after the polyacrylonitrile fiber is heated, the composite fiber is not easy to reach the thermal cracking temperature, and the combustible gas released by cracking is difficult to reach the burning point. In addition, the alkali can also roughen the surface of the polyacrylonitrile molecular structure, generate grooves and pits and enhance the water absorption effect of the polyacrylonitrile molecular structure. Then the polyacrylonitrile with carboxyl is esterified with glycerol to obtain the product with hydroxyl which can react with 2,4,8, 10-tetraoxy-3, 9-diphosphospiro [5,5]]Carboxyl reaction of undecane-3, 9-dioxo-3, 9-dipropionic acid. The raw materials of the glycerol are easy to obtain, and the reaction steps are simple. Finally, the polyacrylonitrile graft product with hydroxyl is grafted with 2,4,8, 10-tetraoxy-3, 9-diphosphospiro [5,5]]Undecane-3, 9-dioxideAnd (3) reacting with 3, 9-dipropionic acid to connect with a double-spiro phosphonate flame retardant to obtain the final grafted modified polyacrylonitrile product. Glycerol is a trihydric alcohol, and after two hydroxyl groups are reacted, a free hydroxyl group remains, which can enhance the hygroscopicity. The flame-retardant nanofiber composite material prepared by using the flame-retardant nanofiber composite material is subjected to a vertical combustion test. In the test process, the special material is observed to directly form an expanded carbon layer which is in a closed pore shape, so that combustible gas is effectively prevented from entering and combustion is prevented. According to the thermodynamic theory, the increase of the volume can consume the internal energy of the system, and the consumption of the internal energy inevitably reduces the temperature of the system. Meanwhile, the foaming process is a process of releasing water vapor generated by dehydration and carbonization of alcohol and ester in a flame retardant system and non-combustible gas generated by a gas source. The evaporation of water and gas must also consume the greatest amount of thermal energy to lower the temperature of the system. In addition, the formed compact expanded carbon layer covers the surface of a burning object, thereby effectively preventing combustible gas from entering, insulating heat and oxygen, preventing the lower substrate from continuing to burn, preventing the further burning and achieving the purpose of flame retardance. The polyacrylonitrile can reduce the Van der Waals force among molecules after graft modification, not only can improve the deposition uniformity of the nano-fiber on the base material, but also can improve the compatibility of the nano-fiber and the base material.
Preferably, the methanol for precipitation in the step 1) is 10 times the volume of the reaction solution, and the reaction solution is added dropwise to the stirred methanol. The precipitation effect is good under this condition.
Preferably, the low-melting polymer is added during the electrospinning in the step (2) for blending, and the low-melting polymer is one selected from polyvinylidene fluoride, polycaprolactone, polyvinyl formal and polyvinyl butyral. The low melting point polymer can be fused and bonded on the substrate in the subsequent hot pressing treatment, so that the bonding of the polyacrylonitrile nano fiber and the substrate can be enhanced.
Preferably, the base material in the step (2) includes a woven fabric or a nonwoven fabric made of one or more of polyester fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, and polyimide fibers. The base material can be composed of one or more fibers, the air permeability and the filtering property of the base material are different in different weaving modes, and the thickness of the base material can be selected according to application requirements.
Preferably, in the step (4), the inert gas is one or more selected from nitrogen, argon and carbon dioxide.
The invention also provides a device for the preparation method, which comprises a winding device, and an electrostatic spinning machine, a hot press, a hot box and a hot press roller which are sequentially arranged in the horizontal direction, wherein the winding device comprises an unwinding roller, a winding roller and a guide roller, the unwinding roller is positioned on one side of the electrostatic spinning machine, a base material is wound on the unwinding roller, the guide roller is positioned on one side of the hot box, and the base material sequentially passes through the electrostatic spinning machine, the hot press, the hot box and the hot press roller under the action of the guide roller. According to the invention, the textile fiber is taken as a base material and passes through the electrostatic spinning machine, the electrostatic spinning machine ejects polyacrylonitrile nano-fiber with small diameter and large surface area, the polyacrylonitrile nano-fiber can be uniformly deposited on the base material, and then the composite material is combined together by hot pressing of the hot press, so that the nano-fiber attached to the base material can not slide in the wearing and washing processes, the microporous structure can not be damaged, and the waterproof breathable fabric has excellent washing resistance. And then the composite material is subjected to preoxidation treatment by a hot box to enable polyacrylonitrile to have flame retardance, and is subjected to secondary hot-pressing forming by a hot-pressing roller, and finally wound and wound by a winding device.
Therefore, the invention has the following beneficial effects: (1) the invention adopts the electrostatic spinning technology, combines common textile fibers and nano fibers, and leads the composite material to have flame retardance and flame resistance through hot-press shaping and pre-oxidation treatment; (2). The nano-fiber prepared by the electrostatic spinning method has the advantages of small diameter, large specific surface area, high porosity and internal randomly crossed network structure, so that the nano-fiber has excellent filtering performance and strong adsorption capacity to smoke and harmful gas while being flame-retardant; (3) the nano composite fiber material also has the characteristics of low price, green and environment-friendly preparation method, safety and controllability, and suitability for large-scale production.
Drawings
FIG. 1 is a schematic view of a production apparatus of the present invention.
FIG. 2 is a schematic view of a flame retardant nanofiber composite made in accordance with the present invention.
In the figure: 1. the device comprises a winding device, 11, an unwinding roller, 12, a guide roller, 13, a winding roller, 2, an electrostatic spinning machine, 21 a receiving screen, 22, an ejector, 3, a hot press, 31, a hot press roller, 4, a hot box, 5, spinning liquid, 6, a base material, 61, a polyester fiber layer, 62, a polyamide fiber layer and 7 nanometer fiber layers.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
As shown in fig. 1, the manufacturing device of the present invention includes a winding device 1, and an electrostatic spinning machine 2, a hot press 3, a hot box 4, and a hot press roller 31 sequentially disposed from left to right, where the winding device 1 includes an unwinding roller 11, a winding roller 13, and a guide roller 12, the unwinding roller 11 is located at the left side of the electrostatic spinning machine 2, a substrate 6 is wound on the unwinding roller 11, the winding roller 13 is located at the right side of the hot box 4, and the substrate 6 sequentially passes through the electrostatic spinning machine 2, the hot press 3, the hot box 4, and the hot press roller 31 under the action of the guide roller 12. Electrostatic spinning machine 2 includes the measuring pump, sprayer 22 and receipt screen 21, spinning liquid 5 passes through the measuring pump and carries to sprayer 22 one end, substrate 6 is through sprayer 22 and receive between the screen 21, spinning liquid 5 jets the nanofiber that the diameter is little, the surface area is big through sprayer 22, even deposit forms combined material on substrate 6, again with this combined material through 3 hot pressing complex of hot press together, in the dress and the washing process, nanofiber layer 7 attached to on substrate 6 can not slide, little porous structure can not receive the destruction, combined material's waterproof ventilative surface fabric washing resistance is very excellent. And then the composite material is subjected to preoxidation treatment by a hot box 4 to enable polyacrylonitrile to have flame retardance, is subjected to secondary hot-pressing forming by a hot-pressing roller 31, and is finally wound and wound by a winding roller 13.
Example 1
Preparing a spinning solution: dissolving polyacrylonitrile powder in N, N-dimethylformamide, stirring at constant temperature for 24 h at 50 ℃ in water bath to uniformly mix the polyacrylonitrile powder and the dimethylformamide to prepare the polyacrylonitrile electrostatic spinning solution 5 with the mass fraction of 12%.
Electrostatic spinning: the spinning solution 5 is conveyed to one end of an ejector 22, the conveying speed of a metering pump is set at 5.0 ml/min, polyester fiber non-woven fabric is selected as a base material 6, the spinning voltage is adjusted to be 30 kV, the receiving distance is 15 cm, and the average diameter of the prepared nano fiber is 300 +/-10 nm.
Hot-pressing and shaping: and (3) conveying the polyester fiber non-woven fabric sprayed with the nanofibers into a hot press 3, setting the hot pressing temperature at 60 ℃, the hot pressing time at 3 min and the hot pressing pressure at 20 MPa to obtain the double-layer composite material consisting of the polyacrylonitrile nanofibers and the polyester fibers.
Pre-oxidation treatment: the composite material after hot pressing and shaping is sent into a hot box 4, in order to prevent the base material 6 from being thermally decomposed at high temperature, a low-temperature pre-oxidation mode is adopted in inert gas nitrogen, the temperature gradient is set between 220 ℃ and 230 ℃, the hot box 4 can be divided into a plurality of layers, and the pre-oxidation time is 15 min.
(5) Winding to form a material: and conveying the pre-oxidized composite material to a hot pressing roller 31 through a guide roller 12 for secondary hot pressing and shaping, wherein the hot pressing temperature is 70 ℃, the hot pressing pressure is 10 MPa, and then winding and collecting are carried out at the speed of 0.3 m/min. The structure of the obtained flame retardant nanofiber composite is shown as a in fig. 2, and consists of a polyester fiber layer 61 and a nanofiber layer 7.
Example 2
Preparing a spinning solution: and (3) dissolving polyacrylonitrile powder in N, N-dimethylformamide, and stirring at a constant temperature for 24 hours at a water bath temperature of 50 ℃ to uniformly mix the polyacrylonitrile powder and the dimethylformamide to prepare the polyacrylonitrile electrostatic spinning solution 5 with the mass fraction of 14%.
Electrostatic spinning: the spinning solution 5 is conveyed to one end of an ejector 22, the conveying speed of a metering pump is set at 5.0 ml/min, a fabric formed by blending polyester fibers and polyamide fibers is selected as a base material 6, the spinning voltage is adjusted to be 32 kV, the receiving distance is 14 cm, and the average diameter of the prepared nano fibers is 311 +/-10 nm.
Hot-pressing and shaping: and (3) conveying the cloth sprayed with the nanofibers into a hot press 3, setting the hot pressing temperature at 60 ℃, the hot pressing time at 3 min and the hot pressing pressure at 25 MPa to obtain the double-layer composite material consisting of the polyacrylonitrile nanofibers and the blended cloth.
Pre-oxidation treatment: the composite material after hot pressing and shaping is sent into a hot box 4, in order to prevent the base material 6 from being thermally decomposed at high temperature, a low-temperature pre-oxidation mode is adopted in inert gas argon, the temperature gradient is set between 200 and 210 ℃, the hot box 4 can be divided into a plurality of layers, and the pre-oxidation time is 20 min.
Winding to form a material: and conveying the pre-oxidized composite material to a hot pressing roller 31 through a guide roller 12 for secondary hot pressing and shaping, wherein the hot pressing temperature is 75 ℃, the hot pressing pressure is 10 MPa, and then winding and collecting are carried out at the speed of 0.2 m/min.
Example 3
(1) Preparing a spinning solution: dissolving polyacrylonitrile powder in N, N-dimethylformamide, stirring at constant temperature for 24 h at 50 ℃ in water bath to uniformly mix the polyacrylonitrile powder and the N, N-dimethylformamide to prepare 14 mass percent polyacrylonitrile electrostatic spinning solution 5, and dissolving polyvinylidene fluoride in N, N-dimethylformamide to prepare 10 mass percent polyvinylidene fluoride electrostatic spinning solution.
(2) Electrostatic spinning: and respectively conveying the polyacrylonitrile spinning solution 5 and the polyvinylidene fluoride spinning solution to one end of different ejectors 22, wherein the conveying speed of a metering pump of the polyacrylonitrile spinning solution 5 is 5.0 ml/min, and the conveying speed of a metering pump of the polyvinylidene fluoride spinning solution is 1.0 ml/min. Selecting a polyester fiber woven fabric as a base material 6, adjusting the spinning voltage to be 32 kV, adjusting the receiving distance to be 14 cm, and adjusting the average diameter of the prepared composite nanofiber to be 311 +/-10 nm.
(3) Hot-pressing and shaping: and (3) conveying the polyester fiber cloth sprayed with the composite nanofibers into a hot press 3, setting the hot pressing temperature at 100 ℃, the hot pressing time at 2 min and the hot pressing pressure at 10 MPa to obtain the double-layer composite material formed by the nanofibers and the polyester fiber cloth. The polyvinylidene fluoride nano-fibers are melted after the hot pressing treatment to form a large number of bonding points, so that the strength of the electrostatic spinning nano-fibers and the bonding between the fibers and the base material 6 are greatly improved.
(4) Pre-oxidation treatment: the composite material after hot pressing and shaping is sent into a hot box 4, in order to prevent the base material 6 from being thermally decomposed at high temperature, a low-temperature pre-oxidation mode is adopted in inert gas carbon dioxide, the temperature gradient is set between 200 and 210 ℃, the hot box 4 can be divided into a plurality of layers, and the pre-oxidation time is 20 min.
(5) Winding to form a material: and conveying the pre-oxidized composite material to a hot pressing roller 31 through a guide roller 12 for secondary hot pressing and shaping, wherein the hot pressing temperature is 70 ℃, the hot pressing pressure is 15 MPa, and then winding and collecting are carried out at the speed of 0.3 m/min.
Example 4
Preparing a spinning solution: dissolving polyacrylonitrile powder in N, N-dimethylformamide, stirring at constant temperature for 24 h at 50 ℃ in water bath to uniformly mix the polyacrylonitrile powder and the N, N-dimethylformamide to prepare 14 mass percent polyacrylonitrile electrostatic spinning solution 5, and dissolving polyvinylidene fluoride in N, N-dimethylformamide to prepare 10 mass percent polyvinylidene fluoride electrostatic spinning solution.
Electrostatic spinning: and respectively conveying the polyacrylonitrile spinning solution 5 and the polyvinylidene fluoride spinning solution to one end of different ejectors, wherein the conveying speed of a metering pump of the polyacrylonitrile spinning solution 5 is 5.0 ml/min, and the conveying speed of a metering pump of the polyvinylidene fluoride spinning solution is 1.0 ml/min. Selecting a polyester fiber woven fabric as a base material 6, adjusting the spinning voltage to be 32 kV, adjusting the receiving distance to be 14 cm, and adjusting the average diameter of the prepared composite nanofiber to be 311 +/-10 nm.
Hot-pressing and shaping: and combining the polyester fiber cloth and the polyamide fiber cloth on which the composite nanofibers are sprayed, conveying the combined material into a hot press 3, setting the hot pressing temperature at 60 ℃, the hot pressing time at 3 min and the hot pressing pressure at 20 MPa, and obtaining the three-layer composite material consisting of the polyester fiber cloth, the nanofibers and the polyamide fibers. The polyvinylidene fluoride nano-fibers are melted after the hot pressing treatment to form a large number of bonding points, so that the strength of the electrostatic spinning nano-fibers and the bonding between the fibers and the base material 6 are greatly improved.
Pre-oxidation treatment: the composite material after hot pressing and shaping is sent into a hot box 4, in order to prevent the base material 6 from being thermally decomposed at high temperature, a low-temperature pre-oxidation mode is adopted in inert gas consisting of nitrogen and argon in a ratio of 1:1, the temperature gradient is set between 200 ℃ and 210 ℃, the hot box 4 can be divided into a plurality of layers, and the pre-oxidation time is 20 min.
Winding to form a material: and conveying the pre-oxidized composite material to a hot pressing roller 31 through a guide roller 12 for secondary hot pressing and shaping, wherein the hot pressing temperature is 70 ℃, the hot pressing pressure is 15 MPa, and then winding and collecting are carried out at the speed of 0.3 m/min. The structure of the prepared flame-retardant nanofiber composite material is shown as b in fig. 2, and the flame-retardant nanofiber composite material is formed by sequentially bonding a polyester fiber layer 61, a nanofiber layer 7 and a polyamide fiber layer 62.
Example 5
(1) Modification treatment of polyacrylonitrile: 1) mixing polyacrylonitrile, sodium hydroxide and water according to the mass ratio of 1:6:40, carrying out reflux reaction for 22 hours, adjusting the reaction liquid to be neutral by using hydrochloric acid, dropwise adding the reaction liquid into stirred methanol for precipitation, wherein the volume of the methanol is 10 times of that of the reaction liquid, filtering, washing with the methanol, and drying to obtain a product a;
2) mixing the product a, glycerol and N, N-dimethylformamide according to the mass ratio of 50:9:50, and reacting at 100 ℃ for 12 hours to obtain a product b;
3) and mixing the product b, 2,4,8, 10-tetraoxy-3, 9-diphosphspiro [5,5] undecane-3, 9-dioxo-3, 9-dipropionic acid and water according to the mass ratio of 1:2:2, and reacting at 90 ℃ to obtain the modified polyacrylonitrile.
(2) Preparing a spinning solution: and (2) dissolving the modified polyacrylonitrile powder in N, N-dimethylformamide, and stirring at a constant temperature of 40 ℃ for 24 hours to uniformly mix the powder and the dimethylformamide to prepare the polyacrylonitrile electrostatic spinning solution 5 with the mass fraction of 20%.
(3) Electrostatic spinning: the spinning solution 5 is conveyed to one end of an ejector 22, the conveying speed of a metering pump is set at 5.0 ml/min, polyester fiber non-woven fabric is selected as a base material 6, the spinning voltage is adjusted to be 50 kV, the receiving distance is 50 cm, and the average diameter of the prepared nano fiber is 50 +/-10 nm.
(4) Hot-pressing and shaping: and (3) conveying the polyester fiber non-woven fabric sprayed with the nanofibers into a hot press 3, setting the hot pressing temperature to be 80 ℃, the hot pressing time to be 1 min and the hot pressing pressure to be 100 MPa, thus obtaining the double-layer composite material consisting of the polyacrylonitrile nanofibers and the polyester fibers.
(5) Pre-oxidation treatment: the composite material after hot pressing and shaping is sent into a hot box 4, in order to prevent the base material 6 from being thermally decomposed at high temperature, a low-temperature pre-oxidation mode is adopted in inert gas nitrogen, the temperature gradient is set between 230 ℃ and 240 ℃, the hot box 4 can be divided into a plurality of layers, and the pre-oxidation time is 10 min.
Example 6
(1) Modification treatment of polyacrylonitrile: 1) mixing polyacrylonitrile, sodium hydroxide and water according to the mass ratio of 3:6:60, carrying out reflux reaction for 24 hours, adjusting the reaction liquid to be neutral, precipitating with methanol, washing and drying to obtain a product a; 2) mixing the product a, glycerol and N, N-dimethylformamide according to the mass ratio of 50:15:80, and reacting at 120 ℃ for 8 hours to obtain a product b; 3) and mixing the product b, 2,4,8, 10-tetraoxy-3, 9-diphosphspiro [5,5] undecane-3, 9-dioxo-3, 9-dipropionic acid and water according to the mass ratio of 1:4:6, and reacting at 90 ℃ to obtain the modified polyacrylonitrile.
(2) Preparing a spinning solution: and (3) dissolving polyacrylonitrile powder in N, N-dimethylformamide, and stirring at a constant temperature of 60 ℃ for 20 hours to uniformly mix the polyacrylonitrile powder and the dimethylformamide to prepare the polyacrylonitrile electrostatic spinning solution 5 with the mass fraction of 8%.
(3) Electrostatic spinning: the spinning solution 5 is conveyed to one end of an ejector 22, the conveying speed of a metering pump is set at 5.0 ml/min, polyester fiber non-woven fabric is selected as a base material 6, the spinning voltage is adjusted to be 20 kV, the receiving distance is 18 cm, and the average diameter of the prepared nano fiber is 1000 +/-10 nm.
(4) Hot-pressing and shaping: and (3) conveying the polyester fiber non-woven fabric sprayed with the nanofibers into a hot press 3, setting the hot pressing temperature at 70 ℃, the hot pressing time at 2 min and the hot pressing pressure at 50 MPa to obtain the double-layer composite material consisting of the polyacrylonitrile nanofibers and the polyester fibers.
(5) Pre-oxidation treatment: the composite material after hot pressing and shaping is sent into a hot box 4, in order to prevent the base material 6 from being thermally decomposed at high temperature, a low-temperature pre-oxidation mode is adopted in inert gas nitrogen, the temperature gradient is set between 220 ℃ and 230 ℃, the hot box 4 can be divided into a plurality of layers, and the pre-oxidation time is 10 min.
Example 7
(1) Modification treatment of polyacrylonitrile: 1) mixing polyacrylonitrile, sodium hydroxide and water according to the mass ratio of 2:6:50, carrying out reflux reaction for 23 hours, adjusting the reaction liquid to be neutral, precipitating with methanol, washing and drying to obtain a product a; 2) mixing the product a, glycerol and N, N-dimethylformamide according to the mass ratio of 50:12:60, and reacting at 110 ℃ for 10 hours to obtain a product b; 3) and mixing the product b, 2,4,8, 10-tetraoxy-3, 9-diphosphspiro [5,5] undecane-3, 9-dioxo-3, 9-dipropionic acid and water according to the mass ratio of 1:3:4, and reacting at 90 ℃ to obtain the modified polyacrylonitrile.
(2) Preparing a spinning solution: dissolving polyacrylonitrile powder in N, N-dimethylformamide, stirring at constant temperature for 24 h at 50 ℃ in water bath to uniformly mix the polyacrylonitrile powder and the dimethylformamide to prepare the polyacrylonitrile electrostatic spinning solution 5 with the mass fraction of 10%.
(3) Electrostatic spinning: the spinning solution 5 is conveyed to one end of an ejector 22, the conveying speed of a metering pump is set at 5.0 ml/min, polyester fiber non-woven fabric is selected as a base material 6, the spinning voltage is adjusted to be 30 kV, the receiving distance is 10 cm, and the average diameter of the prepared nano fiber is 500 +/-10 nm.
(4) Hot-pressing and shaping: and (3) conveying the polyester fiber non-woven fabric sprayed with the nanofibers into a hot press 3, setting the hot pressing temperature at 60 ℃, the hot pressing time at 5 min and the hot pressing pressure at 1 MPa to obtain the double-layer composite material consisting of the polyacrylonitrile nanofibers and the polyester fibers.
(5) Pre-oxidation treatment: the composite material after hot pressing and shaping is sent into a hot box 4, in order to prevent the base material 6 from being thermally decomposed at high temperature, a low-temperature pre-oxidation mode is adopted in inert gas nitrogen, the temperature gradient is set between 220 ℃ and 230 ℃, the hot box 4 can be divided into a plurality of layers, and the pre-oxidation time is 15 min.
And (3) performance testing: the nanofiber composite prepared above was subjected to a limiting oxygen index test, a peel strength test and a filtration performance test, and the results are shown in the following table. Testing the limiting oxygen index of the nanofiber composite according to GB/T5454-1997 (textile burning performance test oxygen index method); testing the combustion performance and the grade of the flame-retardant material of the nanofiber composite according to the GB/T2408-2008 (horizontal and vertical methods); the nanofiber composite peel strength was tested according to FZ/T64014.5.1-2009 (coated fabric for film construction) standard; the rate of smoke density reduction of the nanofiber composite was tested using a cone calorimeter according to GB/T16172-2007 (building material Heat Release Rate test method).
In the table, the comparative example is a polyester fiber non-woven fabric added with antimony trioxide, the antimony trioxide is generally dispersed in water by a binder and fixed on the polyester fiber by coating, padding, drying and heat setting methods, and compared with the comparative example and the example 1, the flame resistance of the polyester fiber non-woven fabric can be improved and the smoke amount can be greatly reduced by spraying the polyacrylonitrile nano fiber on the surface of the polyester fiber non-woven fabric. Examples 5-7 have modified polyacrylonitrile and from the results it can be seen that this modification is effective in increasing the flame resistance and reducing the amount of smoke of the nanofiber composite.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. The preparation method of the flame-retardant nanofiber composite material is characterized by comprising the following steps of:
(1) preparing a spinning solution: dissolving polyacrylonitrile in N, N-dimethylformamide to prepare polyacrylonitrile spinning solution with the mass fraction of 8% -20%;
(2) electrostatic spinning: adjusting the spinning voltage of an electrostatic spinning machine to be 20-50 kV, spraying the spinning solution to form nano fibers with the diameter of 50-1000 nm, spraying the nano fibers onto a base material, wherein the base material is textile fibers, and the receiving distance of the base material is 10-20 cm;
(3) hot-pressing and shaping: conveying the base material sprayed with the nano fibers into a hot press, controlling the hot pressing temperature at 60-100 ℃, the hot pressing time at 1-5 min, and the hot pressing pressure at 1-100 MPa;
(4) pre-oxidation treatment: sending the hot-pressed and shaped material into a heat box, and carrying out low-temperature pre-oxidation in inert gas for 10-20 min, wherein the temperature is set between 200 ℃ and 240 ℃;
(5) winding to form a material: and (4) carrying out the hot-press forming on the composite material subjected to the pre-oxidation treatment again, and finally winding and collecting.
2. The preparation method of the flame-retardant nanofiber composite material as claimed in claim 1, wherein in the step (1), polyacrylonitrile and N, N-dimethylformamide are mixed and then continuously stirred for 20-24 h in water bath at 40-60 ℃.
3. The preparation method of the flame-retardant nanofiber composite material as claimed in claim 1, wherein the polyacrylonitrile subjected to the modification treatment in the step (1) comprises the following steps:
1) mixing polyacrylonitrile with sodium hydroxide according to the mass ratio of (1-3) to (6) (40-60), refluxing for 22-24 h, adjusting the reaction liquid to be neutral, precipitating with methanol, washing and drying to obtain a product a;
2) mixing the product a, glycerol and N, N-dimethylformamide according to the mass ratio of 50 (9-15) to (50-80), and reacting at the temperature of 100 ℃ and 120 ℃ for 8-12 h to obtain a product b;
3) and mixing the product b, a double-spiro phosphonate flame retardant and water according to the mass ratio of 1 (2-4) to (2-6), and reacting at 90 ℃ to obtain the modified polyacrylonitrile, wherein the double-spiro phosphonate flame retardant is 2,4,8, 10-tetraoxy-3, 9-diphosphospiro [5,5] undecane-3, 9-dioxo-3, 9-dipropionic acid.
4. The method of claim 3, wherein the methanol used for precipitation in step 1) is 10 times the volume of the reaction solution, and the reaction solution is added dropwise to the stirred methanol.
5. The preparation method of the flame-retardant nanofiber composite material as claimed in claim 1, wherein a low-melting polymer is added during the electrospinning in the step (2) for blending, and the low-melting polymer is selected from one of polyvinylidene fluoride, polycaprolactone, polyvinyl formal and polyvinyl butyral.
6. The method of claim 1, wherein the substrate in step (2) comprises a woven fabric or a non-woven fabric made of one or more of polyester fiber, polyamide fiber, polyacrylonitrile fiber, polyurethane fiber, and polyimide fiber.
7. The method for preparing a flame retardant nanofiber composite as claimed in claim 1 or 5 or 6, wherein in the step (4), the inert gas is selected from one or more of nitrogen, argon and carbon dioxide.
8. A preparation device for the flame-retardant nanofiber composite material according to any one of claims 1 to 7, characterized by comprising a winding device (1) and an electrostatic spinning machine (2), a hot press (3), a hot box (4) and a hot pressing roll (31) which are sequentially arranged in the horizontal direction, wherein the winding device (1) comprises an unwinding roll (11), a winding roll (13) and a guide roll (12), the unwinding roll (11) is positioned on one side of the electrostatic spinning machine (2), a substrate (6) is wound on the unwinding roll (11), the winding roll (13) is positioned on one side of the hot box (4), and the substrate (6) sequentially passes through the electrostatic spinning machine (2), the hot press (3), the hot box (4) and the hot pressing roll (41) under the action of the guide roll (12).
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