CN107326653B - Ultra-high-flux nanofiber waterproof breathable film and preparation method thereof - Google Patents
Ultra-high-flux nanofiber waterproof breathable film and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- 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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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- 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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- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
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- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/24—Polymers or copolymers of alkenylalcohols or esters thereof; Polymers or copolymers of alkenylethers, acetals or ketones
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/38—Polyurethanes
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Abstract
The invention relates to an ultra-high-flux nanofiber waterproof breathable film and a preparation method thereof, belonging to the field of synthesis of textile technical materials. The ultrahigh-flux nanofiber waterproof breathable film is prepared from the following two components: bifunctional group modified nano silicon dioxide particles and polymer nanofiber membranes. The nano fiber membrane adopts bifunctional group modified nano particles as an adhesion agent among fibers, so that the rubbing resistance of a membrane material can be enhanced, the roughness of the surface of the nano fibers can be increased, and the waterproofness of the fiber membrane can be increased. The ultrahigh-flux waterproof moisture-permeable functional film prepared by the invention has small aperture, high porosity and enhanced adhesion structure, has the characteristics of high water pressure resistance, high moisture-permeable flux and high strength when being used in the field of waterproof moisture-permeable, and the moisture-permeable flux is more than or equal to 18000g/m2And/d, the water pressure resistance is more than or equal to 100kPa, and the method has wide practical application prospect.
Description
Technical Field
The invention relates to a waterproof breathable film, in particular to an ultrahigh-flux nanofiber waterproof breathable film and a preparation method thereof.
Background
Waterproof and Moisture Permeable Fabric (Waterprof & Moisture Permeable Fabric) is also commonly called Waterproof and Breathable Fabric, is generally called Breathable Fabric (Waterprof but Breathable Fabric) abroad, and is a Fabric which can prevent rain, sweat and ventilate. It is present in the situation of increasing self-protection of humans against the aggression of the nature. In the wearing process, water cannot permeate the fabric under certain pressure, sweat emitted by a human body can be conducted to the outside through the fabric in the form of water vapor, condensation and accumulation between the surface of the human body and the fabric are avoided, and a wearer is kept dry and warm. Therefore, it is called "breathable fabric" abroad. The fabric can meet the wearing requirements of people in severe environments such as severe cold, rain, snow, strong wind and the like during activities, is also suitable for the daily life requirements of people, and has wide development prospect.
Waterproof moisture permeable fabrics are mainly realized by using huge difference of water vapor molecules and water molecules, if a certain 'hole' is formed on the fabric, and the size of the hole is between that of a water drop and the water vapor molecule, the fabric can only allow the water vapor molecule to pass through, and the water drop is prevented from passing through. The waterproof moisture permeable fabric has the following three preparation ways: 1) a water repellent treated high density fabric; 2) laminating the fabric; 3) coating the fabric. The high-density fabric has complex production process, high cost and less ideal waterproof and moisture-permeable performance. The other is coated fabric, and although the breathable fabric is simple in process and low in cost, the waterproof and moisture-permeable performance is poor. The mainstream technology in the market at present is a laminated composite material of an ePTFE (expanded polytetrafluoroethylene) microporous membrane and a fabric of Gore-Tex (Goerts) in the United states, the waterproof moisture-permeable fabric prepared by the technology has better waterproof moisture-permeable performance, but special biaxial stretching equipment is needed for preparation, the process is complex, the product processing difficulty is high, the cost is high, the product price is high, and the popularization and application of the fabric are limited to a great extent.
Related reports on waterproof breathable fibers also exist in the prior art:
patent CN102632648A proposes that at room temperature, polyurethane is added into a solvent, and then hydrophobic nanoparticles are added to obtain a spinning solution with uniform properties; carrying out ultrasonic treatment on the spinning solution, carrying out electrostatic spinning on the spinning solution after the ultrasonic treatment, and obtaining an electrostatic spinning nanofiber membrane on a receiving device; the adhesive is transferred to the electrostatic spinning nanofiber membrane in a dotted form through a transfer roller to form an adhesive dotted adhesive layer, the fiber fabric is adhered to form a fiber fabric layer, then hot rolling is carried out to prepare the high-efficiency waterproof moisture-permeable fabric, and the nanofiber prepared through electrostatic spinning is used for preparing the waterproof moisture-permeable fabric.
Patent CN201410148615.9 discloses a waterproof moisture permeable composite membrane and a preparation method thereof, wherein the waterproof moisture permeable composite membrane comprises a hydrophobic membrane and a hydrophilic membrane, a polyester thermoplastic membrane (TPEE membrane) is used as a receiving substrate, hydrophobic polymer spinning solution is stretched into nano/submicron fibers by utilizing an electrostatic spinning nanotechnology, and the nano/submicron fibers are deposited on a non-porous membrane to form a composite membrane of 'hydrophilic membrane + microporous membrane'.
Patent CN105568556A discloses a method for preparing a superhydrophobic or superhydrophilic antibacterial nanofiber membrane, which comprises the following steps: preparing a polymer solution; step (2), electrostatic spinning; preparing a quaternary ammonium salt solution; preparing a suspension mixed solution of quaternary ammonium salt and nano particles; step (5) modifying the porous nanofiber membrane by using a suspension mixed solution of quaternary ammonium salt and nanoparticles; and (6): and (3) placing the porous nanofiber membrane modified by the suspension mixed solution of the quaternary ammonium salt and the nanoparticles prepared in the step (5) in a vacuum oven at 60 ℃ for drying for 1-3h to prepare a finished product of the superhydrophobic or superhydrophilic nanofiber membrane with antibacterial performance. The patent only modifies the nanofiber membrane by utilizing super-hydrophobic or super-hydrophilic nanoparticles, and the surface of the nanoparticles only has hydrophilic or hydrophobic groups, so that the waterproof and moisture permeable effects of the fabric cannot be met.
The nanofiber membrane prepared by electrostatic spinning has high porosity and good waterproof and moisture-permeable performances because the fiber diameter is in a nanoscale, but the method provided by the prior art is generally based on hydrophobic polymers, the solvents of polymer spinning solutions are all organic solvents, polluted gas can be formed in the spinning process, and the nanofiber formed by direct spinning has a smooth surface and does not have a rough structure similar to the lotus leaf surface, so that the nanofiber membrane prepared directly has insufficient waterproof capacity. And the toughness and the kneadable performance of the nanofiber membrane are poor, acting force between fibers can be increased through hot pressing and glue adding layers, the toughness of the fiber membrane is enhanced, but the original fiber structure can be damaged, and the porosity of the original fiber membrane is reduced. Therefore, the invention provides a method for solving the technical defects of poor waterproof and moisture-permeable performance, complex preparation process, complex process, rubbing resistance and the like in the prior art.
Disclosure of Invention
In order to solve the problems of poor waterproof and moisture permeable performance, complex preparation process, complex process, rubbing resistance and the like of the waterproof and breathable film in the prior art, the invention provides an ultrahigh-flux nanofiber waterproof and breathable film and a preparation method thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
on one hand, the invention provides an ultrahigh-flux nanofiber waterproof breathable film which is prepared from the following components in percentage by weight:
1-10 percent of nano silicon dioxide particles modified by bifunctional groups
The balance of the polymer nanofiber membrane.
Further, the ultrahigh-flux nanofiber waterproof breathable film is prepared from the following components in percentage by weight:
2 to 5 percent of nano silicon dioxide particles modified by bifunctional groups
The balance of the polymer nanofiber membrane.
The bifunctional group is a grafting group and a hydrophobic group; the grafting group comprises carboxyl, amino, sulfydryl, aldehyde group or epoxy group; the hydrophobic group includes a polyoxypropylene group, a long-chain perfluoroalkyl group, a polysiloxane group, or a long-chain hydrocarbon group.
Further, in the step 1, the grafting group is generated by silane coupling agent dihydro-3- [3- (trimethoxysilyl) propyl ] furan-2, 5-dione, 3- (2,3 glycidoxypropyl) triethoxysilane, gamma-aminopropyltriethoxysilane or 3-mercaptopropyltriethoxysilane;
the hydrophobic group is hexadecyl trimethoxy silane, dodecyl trimethoxy silane, tridecafluorooctyl trimethoxy silane, vinyl triethoxy silane or n-butyl triethoxy silane.
It should be noted that the above-mentioned silane coupling agents are only a few examples of the present invention, and any silane coupling agent capable of generating a carboxyl group, an amino group, a mercapto group, an aldehyde group, an epoxy group, or the like as a graft group can be used in the present invention; silane coupling agents that can generate hydrophobic groups such as polyoxypropylene groups, long-chain perfluoroalkyl groups, polysiloxane groups, or long-chain hydrocarbon groups can be used in the present invention.
The surface of the nano silicon dioxide particles is modified with two functional groups, the grafting group can chemically react with the functional groups on the surface of the fibers, and after the particles and the fibers which are in contact with each other are grafted simultaneously, the acting force between the fibers can be enhanced, and the toughness of the fiber membrane can be enhanced; the hydrophobic groups have strong hydrophobicity, a coarse structure similar to a lotus leaf surface is formed on the fiber surface, and the waterproofness of the waterproof moisture-permeable membrane is enhanced, so that the roughness of the fiber surface is increased, the bonding effect among fibers is increased and the rubbing resistance of the fibers is enhanced under the condition of ensuring the fluffy state of the original nanofiber membrane. The method greatly breaks through the limitation of the existing materials for preparing the waterproof moisture-permeable membrane, is not limited by hydrophobic high molecular polymers such as Polyurethane (PU), polytetrafluoroethylene and the like any more, and some hydrophilic environment-friendly polymers can also be used for preparing the waterproof moisture-permeable membrane material.
Further, the diameter of the bifunctional group modified nano silicon dioxide particle is 5nm-100 nm.
Further, the polymer nanofiber membrane is made of one or more of polyurethane, organic silicon-acrylate copolymer, polyacrylate, organic silicon, polystyrene, polyvinyl acetate, polylactic acid-caprolactone, polyacrylonitrile, polylactic acid-polyoxyethylene, polyurethane-acrylate, polyvinyl alcohol, styrene-acrylate copolymer, chitosan, vinyl acetate-acrylate copolymer, cellulose acetate, polytetrafluoroethylene, fibroin fiber and polyamide.
Further, the thickness of the polymer fiber film is 1-50 μm.
On the other hand, the invention also provides a preparation method of the ultrahigh-flux nanofiber waterproof breathable film, which comprises the following steps:
step 1: preparing surface bifunctional group modified nano silicon dioxide particles by a method of alternately adding different silane coupling agents for grafting;
step 2: preparing a polymer solution, and preparing a nanofiber membrane by an electrostatic spinning process;
and step 3: and (3) chemically grafting the bifunctional group modified nano silicon dioxide particles prepared in the step (1) on the nano fibers.
Further, in the step 3, the nanofiber membrane is subjected to surface modification treatment before being grafted with the nano silica particles, and functional groups on the surface of the nanofiber membrane after the treatment can be subjected to grafting reaction with the nano silica particles modified by the bifunctional groups.
Further, in the step 3, the processing method of the chemical grafting of the bifunctional group modified nano silica particles is one or more of dip coating, brush coating and spray coating, and then the nano silica is promoted to be fixed on the surface of the fiber by one or more of heating, illumination, radiation, microwave or ultrasonic processing.
The invention provides an ultrahigh-flux nanofiber waterproof breathable film and a preparation method thereof, and the ultrahigh-flux nanofiber waterproof breathable film has the following beneficial effects:
1) the method avoids the problems of damage and reduction of the surface gap of the fiber membrane caused by adding point glue, hot pressing and other methods, maintains the loose state of the nanofiber membrane, and improves the air permeability of the fiber membrane;
2) the nano silicon dioxide particles modified by the bifunctional groups are prepared, and the long-chain or fluorine-containing hydrophobic group modified nano particles increase the roughness of the fiber surface, increase the hydrophobicity of the fiber and greatly improve the water resistance of the fiber membrane surface;
3) the grafting group is a crosslinking group to crosslink the fibers which are mutually contacted in the fiber membrane together, so that the structure among the fibers is fixed, and the toughness and the rubbing resistance of the fiber membrane are improved;
4) the prepared nanoparticles with the bifunctional groups can be chemically grafted on the surface of a hydrophilic fiber membrane, so that the raw material selection range of the waterproof moisture-permeable membrane material is expanded, the pollution of an organic solvent to the environment is reduced, and the preparation method has good environmental protection significance;
5) the ultrahigh-flux waterproof breathable film prepared by the method has small aperture, high porosity and enhanced adhesion structure, and has high water pressure resistance and permeability when being used in the field of waterproof and moisture permeableHigh wet flux (not less than 18000 g/m)2And/d, the water pressure resistance is more than or equal to 100kPa, and the method has wide practical application prospect.
Drawings
FIG. 1 is an SEM photograph of a bifunctional group-modified silica/polyvinyl alcohol nanofiber spinning membrane of example 1 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.
The above-described scheme is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes and are not intended to limit the scope of the present invention. The conditions used in the examples may be further adjusted according to the conditions of the particular manufacturer, and the conditions not specified are generally the conditions in routine experiments.
Materials, reagents and the like used in the following examples are commercially available.
The invention provides an ultra-high-flux nanofiber waterproof breathable film and a preparation method thereof, and the specific material dosage and experimental process are shown in the following examples.
Example 1:
an ultra-high flux nano fiber waterproof breathable film and a preparation method thereof comprise the following steps:
step 1: preparing 100g of nano-silica toluene dispersion liquid with the mass concentration of 0.5%, preparing 5g of toluene solution of 10% dihydro-3- [3- (trimethoxysilyl) propyl ] furan-2, 5-dione and 5g of toluene solution of 10% hexadecyl trimethoxy silane, alternately adding the mixture into the nano-silica toluene dispersion liquid for multiple times, standing the mixture overnight after the addition is finished, adding 0.5g of water, and hydrolyzing the dihydro-3- [3- (trimethoxysilyl) propyl ] furan-2, 5-dione to form two carboxyl groups to form the nano-silica toluene dispersion liquid modified by the bifunctional groups;
step 2: preparing a polyvinyl alcohol spinning solution, wherein the solvent is water, the mass concentration is 12%, performing electrostatic spinning, the spinning distance is 15cm, the spinning voltage is 35kv, after preparing a polyvinyl alcohol nanofiber membrane, treating the polyvinyl alcohol nanofiber membrane by a 1% gamma-aminopropyltriethoxysilane ethanol solution, and drying the polyvinyl alcohol nanofiber membrane to obtain an amino-modified polyvinyl alcohol nanofiber membrane;
and step 3: and (2) immersing the amino-modified polyvinyl alcohol nanofiber membrane in the bifunctional group-modified nano silicon dioxide toluene dispersion liquid prepared in the step (1), adding EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) and NHS (N-hydroxysuccinimide), reacting for 12h at room temperature, taking out the fiber membrane, and drying to obtain the ultrahigh-flux nanofiber waterproof breathable membrane.
The content of silicon dioxide in the obtained ultra-high flux waterproof breathable film is 10 percent, the water pressure resistance of the waterproof breathable film is 145kPa, and the moisture permeation flux is 20000g/m2And d, after the kneading test instrument kneads 2000 times, the moisture permeability is reduced by 0.3 percent.
Example 2:
an ultra-high flux nano fiber waterproof breathable film and a preparation method thereof comprise the following steps:
step 1: preparing 100g of nano-silica ethanol dispersion liquid with the mass concentration of 0.5%, then preparing 5g of ethanol solution of 10% gamma-aminopropyltriethoxysilane and 5g of ethanol solution of 10% tridecafluorooctyltrimethoxysilane, and alternately adding the ethanol solution of 10% gamma-aminopropyltriethoxysilane and 5g of ethanol solution of 10% tridecafluorooctyltrimethoxysilane into the nano-silica ethanol dispersion liquid for multiple times to form the nano-silica ethanol dispersion liquid modified by the bifunctional groups;
step 2: preparing a spinning solution of deacetylated 90% chitosan, wherein the solvent is glacial acetic acid, the mass concentration is 9%, performing electrostatic spinning, the spinning distance is 18cm, and the spinning voltage is 70kv to obtain a porous chitosan nanofiber membrane;
and step 3: and (2) spraying the bifunctional group modified nano-silica ethanol dispersion liquid prepared in the step (1) on the surface of a chitosan nano-fiber membrane, drying, and putting the fiber membrane into steam of glutaraldehyde to perform a crosslinking reaction between amino on the surface of chitosan and amino on the surface of silica, thereby obtaining the ultra-high-flux nano-fiber waterproof breathable membrane.
The content of silicon dioxide in the obtained ultrahigh-flux waterproof breathable film is 1 percent, the water pressure resistance of the waterproof breathable film is 121kPa, and the moisture-permeable fluxIs 18000g/m2And d, after the kneading test instrument kneads 2000 times, the moisture permeability is reduced by 1 percent.
Example 3:
an ultra-high flux nano fiber waterproof breathable film and a preparation method thereof comprise the following steps:
step 1: preparing 100g of nano-silica ethanol dispersion liquid with the mass concentration of 0.5%, then preparing 5g of ethanol solution of 10% gamma-aminopropyl triethoxysilane and 5g of ethanol solution of 10% vinyl triethoxysilane, and alternately adding the ethanol solution of 10% vinyl triethoxysilane into the nano-silica ethanol dispersion liquid for multiple times to form the nano-silica ethanol dispersion liquid modified by the bifunctional group;
step 2: preparing a polyacrylonitrile spinning solution, wherein a solvent is N, N-dimethylformamide, the mass concentration is 12%, performing electrostatic spinning, the spinning distance is 16cm, the spinning voltage is 60kv, preparing a polyacrylonitrile nanofiber membrane, treating the polyacrylonitrile nanofiber membrane by using a 10% sodium hydroxide solution, cleaning, then adding 15% hydrochloric acid for treatment, and drying to obtain a carboxyl-modified polyacrylonitrile nanofiber membrane with a through hole structure;
and step 3: soaking the carboxyl modified polyacrylonitrile nano-fiber membrane in the bifunctional group modified nano-silica ethanol dispersion liquid, reacting for 24h at 35 ℃, taking out the fiber membrane, irradiating by infrared light, and drying to obtain the ultrahigh-flux nano-fiber waterproof breathable membrane.
The content of silicon dioxide in the obtained ultrahigh-flux waterproof breathable film is 6.8 percent, the water pressure resistance of the waterproof breathable film is 136kPa, and the moisture-permeable flux is 19500g/m2And d, after the kneading test instrument kneads 2000 times, the moisture permeability is reduced by 0.5 percent.
Example 4:
an ultra-high flux nano fiber waterproof breathable film and a preparation method thereof comprise the following steps:
step 1: preparing 100g of nano-silica ethanol dispersion liquid with the mass concentration of 0.5%, preparing 5g of ethanol solution of 10% 3-mercaptopropyltriethoxysilane and 5g of ethanol solution of 10% n-butyltriethoxysilane, and alternately adding the ethanol solution of 10% n-butyltriethoxysilane to the nano-silica ethanol dispersion liquid for multiple times to form the nano-silica ethanol dispersion liquid modified by the bifunctional group;
step 2: preparing a polyurethane-acrylate spinning solution, wherein the solvent is acetone, the mass concentration is 12%, performing electrostatic spinning, the spinning distance is 16cm, the spinning voltage is 60kv, treating the solution by using 1% of gamma-aminopropyltriethoxysilane ethanol solution, and drying the solution to obtain an amino modified polyurethane-acrylate nanofiber membrane;
and step 3: soaking the amino modified polyurethane-acrylate nanofiber membrane in the bifunctional group modified nano silicon dioxide ethanol dispersion liquid, reacting for 24 hours at 35 ℃, taking out the fiber membrane, and drying to obtain the ultrahigh-flux nanofiber waterproof breathable membrane.
The content of silicon dioxide in the obtained ultrahigh-flux waterproof breathable film is 5 percent, the water pressure resistance of the waterproof breathable film is 131kPa, and the moisture permeation flux is 19070g/m2And d, after the kneading test instrument kneads 2000 times, the moisture permeability is reduced by 0.4 percent.
Example 5:
an ultra-high flux nano fiber waterproof breathable film and a preparation method thereof comprise the following steps:
step 1: preparing 100g of nano-silica ethanol dispersion liquid with the mass concentration of 0.5%, then preparing 5g of ethanol solution of 10% gamma-aminopropyl triethoxysilane and 5g of ethanol solution of 10% dodecyl trimethoxy silane, and alternately adding the ethanol solution of 10% gamma-aminopropyl triethoxysilane and 5g of ethanol solution of 10% dodecyl trimethoxy silane into the nano-silica ethanol dispersion liquid for multiple times to form the bifunctional group modified nano-silica ethanol dispersion liquid;
step 2: preparing a spinning solution of a styrene-acrylate copolymer, wherein the solvent is acetone, the mass concentration is 12%, performing electrostatic spinning, the spinning distance is 16cm, the spinning voltage is 60kv, preparing a styrene-acrylate copolymer nanofiber membrane, treating the styrene-acrylate copolymer nanofiber membrane by using a 1% gamma-aminopropyltriethoxysilane ethanol solution, and drying the styrene-acrylate copolymer nanofiber membrane to obtain an amino modified polyvinyl alcohol nanofiber membrane;
and step 3: soaking the carboxyl modified polyurethane-acrylate nanofiber membrane in the bifunctional group modified nano silicon dioxide ethanol dispersion liquid, reacting for 24 hours at 35 ℃, taking out the fiber membrane, heating and drying to obtain the ultrahigh-flux nanofiber waterproof breathable membrane.
The content of silicon dioxide in the obtained ultrahigh-flux waterproof breathable film is 2 percent, the water pressure resistance of the waterproof breathable film is 128kPa, and the moisture-permeable flux is 18750g/m2And d, after the kneading test instrument kneads 2000 times, the moisture permeability is reduced by 0.7 percent.
To further illustrate the performance of the ultra-high flux nanofiber waterproof breathable film prepared by the invention, the invention takes example 3 as an example to construct a comparative example as follows.
Comparative example 1:
a nanofiber membrane and a preparation method thereof, comprising:
step 1: preparing 100g of nano-silica ethanol dispersion liquid with the mass concentration of 0.5%, then preparing 5g of gamma-aminopropyl triethoxysilane ethanol solution with the mass concentration of 10% and 5g of vinyl triethoxysilane ethanol solution with the mass concentration of 10%, and uniformly mixing the three solutions to form modified silica particles;
step 2: and (3) adding an N, N-dimethylformamide solution of polyacrylonitrile with the mass concentration of 12% into the step (1), uniformly stirring to form a spinning solution, wherein the spinning distance is 16cm, and the spinning voltage is 60kv, so as to prepare the modified polyacrylonitrile nanofiber membrane.
The obtained modified polyacrylonitrile nano-fiber membrane has the water pressure resistance of 92kPa and the moisture permeation flux of 8700g/m2And d, after the kneading test instrument kneads 2000 times, the moisture permeability is reduced by 28 percent.
Comparative example 2:
a nanofiber membrane and a preparation method thereof, comprising:
step 1: preparing 100g of nano-silica ethanol dispersion liquid with the mass concentration of 0.5%, then preparing 5g of gamma-aminopropyl triethoxysilane ethanol solution with the mass concentration of 10% and 5g of vinyl triethoxysilane ethanol solution with the mass concentration of 10%, and alternately adding the solutions into the nano-silica ethanol dispersion liquid for multiple times to form the nano-silica ethanol dispersion liquid modified by the bifunctional group;
step 2: and (3) adding an N, N-dimethylformamide solution of polyacrylonitrile with the mass concentration of 12% into the step (1), uniformly stirring to form a spinning solution, wherein the spinning distance is 16cm, and the spinning voltage is 60kv, so as to prepare the modified polyacrylonitrile nanofiber membrane.
The obtained modified polyacrylonitrile nano-fiber membrane has the water pressure resistance of 95kPa and the moisture permeation flux of 9700g/m2And d, after the kneading test instrument kneads 2000 times, the moisture permeability is reduced by 13 percent.
It can be known from the above examples 1-5 and comparative examples 1-2 that the surface bifunctional group modified nano silica particles prepared by the method of grafting by alternately adding different silane coupling agents have greatly improved water pressure resistance, moisture permeation flux and kneading performance compared with the method of adding all silane coupling agents at one time (comparative example 1), which is probably because the first silane coupling agent can continuously modify silica in the gaps when the silica surface is not modified to saturation by alternately adding the silane coupling agents, and the other silane coupling agent can continuously modify silica in the gaps, so that different groups are completely covered on the silica surface after repeated for multiple times, thereby facilitating the subsequent reaction with adjacent fibers, fixing the structure between the fibers and improving the toughness and kneading resistance of the fiber film; meanwhile, the roughness of the fiber surface is increased by more hydrophobic groups, the hydrophobicity of the fiber is increased, and the waterproofness of the fiber membrane surface is greatly improved.
Compared with the comparative example 2, the prepared silica particles modified by the bifunctional groups are modified on the surface of the fiber membrane in the forms of dip coating, brush coating or spray coating, and the obtained ultrahigh-flux nanofiber waterproof breathable membrane has excellent performances. This is probably due to the fact that, on the one hand, no modified silica particles are added to the polymer solution, avoiding the influence of the solvent in the polymer solution on the silica particles; on the other hand, the invention does not need to carry out electrostatic spinning process subsequently, does not have the problem that the surface gap of the fiber membrane is damaged and reduced caused by methods such as hot pressing and the like, keeps the loose state of the nanofiber membrane and improves the air permeability of the fiber membrane.
The experiments are only preferred examples of the present invention and are not intended to limit the scope of the present invention. It should be noted that modifications and adaptations may occur to those skilled in the art without departing from the principles of the present invention and should be considered within the scope of the present invention.
Claims (9)
1. The ultrahigh-flux nanofiber waterproof breathable film is characterized by being prepared from the following components in percentage by weight:
1-10 percent of nano silicon dioxide particles modified by bifunctional groups
The balance of the polymer nanofiber membrane;
the nano silicon dioxide particle modified by the bifunctional group is formed by modifying a grafting group and a hydrophobic group; the grafting group comprises carboxyl, amino, sulfydryl, aldehyde group or epoxy group; the hydrophobic group comprises a polyoxypropylene group, a long-chain perfluoroalkyl group, a polysiloxane group or a long-chain hydrocarbon group;
the polymer nanofiber membrane is prepared from one or more of polyurethane, polyacrylate, organic silicon, polystyrene, polyvinyl acetate, polylactic acid-caprolactone, polyacrylonitrile, polylactic acid-polyoxyethylene, polyvinyl alcohol, chitosan, acetate fiber, polytetrafluoroethylene, fibroin fiber and polyamide;
the bifunctional group modified nano silicon dioxide particles are chemically grafted on the surface of the polymer nanofiber membrane;
the preparation method of the ultrahigh-flux nanofiber waterproof breathable film comprises the following steps:
step 1: preparing surface bifunctional group modified nano silicon dioxide particles by a method of alternately adding silane coupling agent grafting capable of generating a grafting group and a hydrophobic group;
step 2: preparing a polymer solution, preparing nano fibers by an electrostatic spinning process, and then preparing a nano fiber membrane;
and step 3: and (3) chemically grafting the bifunctional group modified nano silicon dioxide particles prepared in the step (1) on the surface of the nanofiber membrane.
2. The ultrahigh-flux nanofiber waterproof breathable film according to claim 1, characterized by being prepared from the following components in percentage by weight:
2 to 5 percent of nano silicon dioxide particles modified by bifunctional groups
The balance of the polymer nanofiber membrane.
3. The ultra-high flux nanofiber waterproof breathable film according to claim 1 or 2, wherein the grafting group is generated by silane coupling agent dihydro-3- [3- (trimethoxysilyl) propyl ] furan-2, 5-dione, 3- (2,3 glycidoxypropyl) triethoxysilane, gamma-aminopropyltriethoxysilane or 3-mercaptopropyltriethoxysilane.
4. The ultra-high throughput nanofiber waterproof breathable film according to claim 1 or 2, wherein the hydrophobic group is produced by hexadecyl trimethoxysilane, dodecyl trimethoxysilane, tridecafluoroctyl trimethoxysilane, vinyl triethoxysilane, or n-butyl triethoxysilane.
5. The ultra-high flux nanofiber waterproof breathable film according to claim 1 or 2, wherein the diameter of the bifunctional group-modified nanosilica particles is 5nm-100 nm.
6. The ultra high flux nanofiber waterproof breathable film according to claim 1 or 2, wherein the polymer fiber film thickness is 1-50 μ ι η.
7. The method of making an ultra-high flux nanofiber waterproof breathable film of any of claims 1 to 6, comprising:
step 1: preparing surface bifunctional group modified nano silicon dioxide particles by a method of alternately adding silane coupling agent grafting capable of generating a grafting group and a hydrophobic group;
step 2: preparing a polymer solution, preparing nano fibers by an electrostatic spinning process, and then preparing a nano fiber membrane;
and step 3: and (3) chemically grafting the bifunctional group modified nano silicon dioxide particles prepared in the step (1) on the surface of the nanofiber membrane.
8. The method for preparing the ultra-high flux nanofiber waterproof breathable film according to claim 7, wherein in the step 3, the nanofiber membrane is subjected to surface modification treatment before being grafted with the bifunctional group-modified nano silica particles, and the functional groups on the surface of the nanofiber membrane can be subjected to grafting reaction with the bifunctional group-modified nano silica particles after the treatment.
9. The method for preparing the ultra-high flux nanofiber waterproof breathable film according to claim 7, wherein in the step 3, the bifunctional group modified nano silica particles are chemically grafted by one or more of dipping, brushing and spraying, and then the nano silica is promoted to be fixed on the fiber surface by one or more of heating, lighting, radiation, microwave or ultrasonic treatment.
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