CN115491818A - Chemically modified electrostatic spinning membrane and preparation method thereof - Google Patents
Chemically modified electrostatic spinning membrane and preparation method thereof Download PDFInfo
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- CN115491818A CN115491818A CN202211181267.6A CN202211181267A CN115491818A CN 115491818 A CN115491818 A CN 115491818A CN 202211181267 A CN202211181267 A CN 202211181267A CN 115491818 A CN115491818 A CN 115491818A
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- flame retardant
- antistatic
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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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- 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
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to the technical field of electrostatic spinning membranes, and discloses a chemically modified electrostatic spinning membrane, which mainly comprises the following components: 65-92 parts of polyurethane prepolymer; 0.25 to 22 portions of antistatic complexing agent; 6-18 parts of flame retardant; 18-24 parts of a stabilizer; the antistatic compounding agent comprises a conjugated polymer material and a metal fiber material, and the flame retardant comprises chlorine flame retardant and bromine flame retardant. The antistatic complexing agent is prepared from a conjugated polymer material and a metal fiber material, pi bond electrons in a long chain of the conjugated polymer material are relatively active and are easy to escape from a track to form free electrons, a conductive energy band is formed to provide a channel for transfer and transition of current carriers, and the antistatic performance is further improved by the aid of the metal antistatic material, so that the antistatic performance of a finished product of a spinning film is effectively improved, the excellent physical performance of the spinning film is combined, the integral using effect of the spinning film is effectively improved, and the comprehensive protection performance of an electronic element is improved.
Description
Technical Field
The invention relates to the technical field of electrostatic spinning membranes, in particular to a chemically modified electrostatic spinning membrane and a preparation method thereof.
Background
In the production process of precision electronic components, in order to ensure the safety of electronic components during transportation or storage, the electronic components are usually covered with a film for protection, and the existing protective film is usually formed by electrostatic spinning, since the electrostatic spinning technology is one of the simplest, efficient and environment-friendly methods nowadays. The spinning film prepared by the electrostatic spinning method has the characteristics of high specific surface area, large length-diameter ratio, cross-linked net structure and the like, so that the material has outstanding effects in the aspects of chemistry, mechanics and the like.
However, although the existing spinning film has good chemical properties and mechanical properties, the antistatic capability of the existing spinning film is not obvious, and the existing spinning film cannot perform substantial antistatic protection on electronic elements, so that the existing protective film has functional defects in the use process, and the protective film is easy to roll up when experiencing high temperature, so that the protective effect of the existing protective film is lost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a chemically modified electrostatic spinning film and a preparation method thereof, and the chemically modified electrostatic spinning film has the advantages of good protection effect, antistatic property and high-temperature release winding.
In order to achieve the purpose, the invention provides the following technical scheme: a chemically modified electrostatic spinning membrane mainly comprises the following components:
65-92 parts of polyurethane prepolymer;
0.25 to 22 portions of antistatic complexing agent;
6 to 18 portions of flame retardant;
18-24 parts of a stabilizer;
the polyurethane prepolymer comprises polyol and isocyanate, the antistatic complexing agent comprises a conjugated polymer material and a metal fiber material, and the flame retardant comprises chlorine flame retardant and bromine flame retardant.
Preferably, the polyhydric alcohol comprises one or any combination mixture of ethylene glycol, 1, 4-butanediol, tetramethyl ether glycol and polyethylene glycol;
the isocyanate is 4,4' -diphenylmethane, diisocyanate or phenyl diisocyanate;
the polyurethane prepolymer is prepared by mixing polyol and isocyanate, wherein the weight ratio of the polyol to the isocyanate is 65-85,
the polyurethane prepolymer is added with one or any combination mixture of 1, 4-butanediol, 1, 3-propanediol or diazobicyclooctane.
Preferably, the conjugated polymer material comprises one or any combination mixture of polyaniline, polyacetylene, polypyridine, polyparaphenylene, polythiophene, polyquinoline and polyparaphenylene sulfide, and the conjugated polymer material further comprises polypyrrole, wherein the weight of the polypyrrole of the conjugated polymer material is 35-45%;
the metal fiber material is lithium oxide fiber and polyethylene glycol/methacrylic acid copolymer particles with the weight ratio of 5-15;
the weight ratio of the conjugated polymer material to the metal fiber material of the antistatic complexing agent is 1.
Preferably, the chlorine-based flame retardant comprises one or any combination mixture of chlorinated polyethylene, tetrachlorophthalic anhydride, tetrachlorobisphenol A and hexachlorocyclopentadiene;
one or any combination mixture of brominated flame-retardant decabromodiphenyl ether, tetrabromophthalic, tetrabromobisphenol A and bromophthalic anhydride;
the flame retardant also comprises magnesium hydroxide and aluminum hydroxide, wherein the weight ratio of the magnesium hydroxide to the aluminum hydroxide is 2-6;
the weight ratio of chlorine flame retardant to bromine flame retardant is 26-32, 48-52, and the total content of magnesium hydroxide and aluminum hydroxide in the flame retardant is 1.2% -2.8%.
Preferably, the stabilizer comprises 60-90 wt% of one or a mixture of hydroxyethyl alkyl imidazoline, N-methyl pyrrolidone, N-dimethyl acetamide, N-dimethyl formamide or dimethyl sulfoxide;
the stabilizer also comprises one or a mixture of hydrophilic polymer polyethylene glycol with molecular weight of 5-30 ten thousand or hydrophilic polymer polyvinylpyrrolidone with K30-K50;
the stabilizer also comprises 2 to 6 percent of one of phenylenediamine or dibutylamine or the mixture thereof;
the rest is 1, 2-ethylene glycol.
A preparation method of a chemically modified electrostatic spinning membrane comprises the following steps:
1) Preparing polyurethane prepolymer, antistatic complexing agent, flame retardant and stabilizer respectively according to the proportion;
2) Stirring and mixing 65-92 parts of polyurethane prepolymer, 0.25-22 parts of antistatic complexing agent, 6-18 parts of flame retardant and 18-24 parts of stabilizer according to the weight ratio of the material prepared in the step 1) to prepare a gel medium;
3) Carrying out electrostatic spinning by using electrostatic spinning equipment;
4) Step 3) spinning yarns are injected into the electrospinning solution by a spinning nozzle to form a film, the spinning voltage is 10-35 KV, the feeding speed is 1-15 mu L/min, the receiving distance is 2-30 cm, and the film forming temperature is 50-60 ℃;
5) Soaking the silk film obtained in the step 4) in a solution containing 1800-2200 ppm of sodium hypochlorite for 3-4 hours, and soaking the silk film in hot water at the temperature of 60-90 ℃ for 15-25 hours to obtain a finished product.
Preferably, the electrospinning solution comprises 5-20% of polymer resin and 0-10% of additive dissolved in 70-95% of solvent by weight ratio to prepare the spinning solution, and the sum of the components is 100%.
Preferably, the polymer resin is at least one of polyacrylonitrile, polyvinylidene fluoride, cellulose acetate, polyvinyl chloride, polyester, polyamide, polypropylene, polysulfone or polyether sulfone; the solvent is at least one of water, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, acetone, tetrahydrofuran or acetic acid; the additive is at least one of polyethylene glycol, polyvinylpyrrolidone, potassium chloride, calcium chloride, sodium chloride, lithium bromide or lithium nitrate.
Has the beneficial effects that:
1. the antistatic complexing agent is prepared from a conjugated polymer material and a metal fiber material, pi bond electrons in long chains of the conjugated polymer material are more active and are easy to escape from a track to form free electrons, a conductive energy band is formed to provide a channel for transfer and transition of current carriers, and the antistatic performance is further improved by the aid of the metal antistatic material, so that the antistatic performance of finished products of the spinning film is effectively improved, the integral using effect of the spinning film is effectively improved by combining the excellent physical performance of the spinning film, and the comprehensive protection performance of electronic elements is improved.
2. According to the chemically modified electrostatic spinning film and the preparation method thereof, the flame retardant is added, so that the high-temperature resistance of the spinning film is improved, compared with the existing protective film, the high-temperature resistance is effectively improved, and the condition of wholly or locally collecting coupons can be avoided under a high-temperature environment or when the protective film is locally contacted with high temperature, so that the protective effect of the spinning film is effectively ensured.
Drawings
FIG. 1 is a schematic view of a spun film of example 1 of the present invention;
FIG. 2 is a schematic infrared spectrum of example 3 of the present invention and a comparative example.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example one
Referring to fig. 1, a method for preparing a chemically modified electrospun membrane includes the following steps:
1) Preparing polyurethane prepolymer, antistatic complexing agent, flame retardant and stabilizer respectively according to the proportion;
the polyurethane prepolymer comprises polyol and isocyanate, the antistatic complexing agent comprises a conjugated polymer material and a metal fiber material, and the flame retardant comprises chlorine flame retardant and bromine flame retardant.
Wherein the polyhydric alcohol comprises one or any combination mixture of ethylene glycol, 1, 4-butanediol, tetramethyl ether glycol and polyethylene glycol;
the isocyanate is 4,4' -diphenylmethane, diisocyanate or phenyl diisocyanate;
the polyurethane prepolymer is prepared by mixing polyol and isocyanate, wherein the weight ratio of the polyol to the isocyanate is 65,
one or any combination mixture of 1, 4-butanediol, 1, 3-propanediol and diazobicyclooctane is added into the polyurethane prepolymer.
The conjugated polymer material comprises one or any combination mixture of polyaniline, polyacetylene, polypyridine, poly-p-phenylene, polythiophene, polyquinoline and poly-p-phenylene sulfide, and also comprises polypyrrole, wherein the weight of the polypyrrole of the conjugated polymer material is 35%;
the metal fiber material is lithium oxide fiber and polyethylene glycol/methacrylic acid copolymer particles with the weight ratio of 5;
the weight ratio of the conjugated polymer material to the metal fiber material of the antistatic complexing agent is 1.
Wherein the chlorine series flame retardant comprises one or any combination mixture of chlorinated polyethylene, tetrachlorophthalic anhydride, tetrachlorobisphenol A and hexachlorocyclopentadiene;
one or any combination mixture of bromine flame-retardant decabromodiphenyl ether, tetrabromophthalic, tetrabromobisphenol A and bromophthalic anhydride;
the flame retardant also comprises magnesium hydroxide and aluminum hydroxide, wherein the weight ratio of the magnesium hydroxide to the aluminum hydroxide is 2;
the weight ratio of the chlorine-series flame retardant to the bromine-series flame retardant of the flame retardant is 26.
Wherein the stabilizer comprises 60 percent by weight of one or a mixture of hydroxyethyl alkyl imidazoline, N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide or dimethyl sulfoxide;
the stabilizer also comprises one or a mixture of hydrophilic polymer polyethylene glycol with molecular weight of 5 ten thousand or hydrophilic polymer polyvinylpyrrolidone with K30-K50;
the stabilizer also comprises 2% of one or the mixture of phenylenediamine and dibutylamine;
the rest is 1, 2-ethylene glycol.
2) Stirring and mixing the polyurethane prepolymer 65, the antistatic complexing agent 0.25, the flame retardant 6 and the stabilizer 18 according to the weight ratio of the material prepared in the step 1) to prepare a gel medium;
3) Carrying out electrostatic spinning by using electrostatic spinning equipment;
4) Step 3) spinning yarns are injected into the electrospinning solution by a spinning nozzle to form a film, the spinning voltage is 10-35 KV, the feeding speed is 115 mu L/min, the receiving distance is 2cm, and the film forming temperature is 50 ℃;
5) And (3) soaking the silk film obtained in the step 4) in a solution containing 1800ppm of sodium hypochlorite for 3 hours, and then soaking the silk film in hot water at the temperature of 60 ℃ for 15 hours to obtain a finished product.
The electrospinning solution comprises 5% of polymer resin dissolved in 95% of solvent by weight ratio to prepare spinning solution.
Wherein the polymer resin is at least one of polyacrylonitrile, polyvinylidene fluoride, cellulose acetate, polyvinyl chloride, polyester, polyamide, polypropylene, polysulfone or polyethersulfone; the solvent is at least one of water, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, acetone, tetrahydrofuran or acetic acid; the additive is at least one of polyethylene glycol, polyvinylpyrrolidone, potassium chloride, calcium chloride, sodium chloride, lithium bromide or lithium nitrate.
Example two
A preparation method of a chemically modified electrostatic spinning membrane comprises the following steps:
1) Preparing polyurethane prepolymer, antistatic complexing agent, flame retardant and stabilizer respectively according to the proportion;
the polyurethane prepolymer comprises polyol and isocyanate, the antistatic complexing agent comprises a conjugated polymer material and a metal fiber material, and the flame retardant comprises chlorine flame retardant and bromine flame retardant.
Wherein the polyhydric alcohol comprises one or any combination mixture of ethylene glycol, 1, 4-butanediol, tetramethyl ether glycol and polyethylene glycol;
the isocyanate is 4,4' -diphenylmethane, diisocyanate or benzene diisocyanate;
the polyurethane prepolymer is prepared by mixing polyol and isocyanate, wherein the weight ratio of the polyol to the isocyanate is 70,
one or any combination mixture of 1, 4-butanediol, 1, 3-propanediol or diazobicyclooctane is added into the polyurethane prepolymer.
The conjugated polymer material comprises one or any combination mixture of polyaniline, polyacetylene, polypyridine, poly-p-phenylene, polythiophene, polyquinoline and poly-p-phenylene sulfide, and also comprises polypyrrole, wherein the weight of the polypyrrole of the conjugated polymer material is 40%;
the metal fiber material is lithium oxide fiber and polyethylene glycol/methacrylic acid copolymer particles with the weight ratio of 10;
the weight ratio of the conjugated polymer material to the metal fiber material of the antistatic complexing agent is 1.
Wherein the chlorine series flame retardant comprises one or any combination mixture of chlorinated polyethylene, tetrachlorophthalic anhydride, tetrachlorobisphenol A and hexachlorocyclopentadiene;
one or any combination mixture of brominated flame-retardant decabromodiphenyl ether, tetrabromophthalic, tetrabromobisphenol A and bromophthalic anhydride;
the flame retardant also comprises magnesium hydroxide and aluminum hydroxide, wherein the weight ratio of the magnesium hydroxide to the aluminum hydroxide is 4;
the weight ratio of the chlorine-series flame retardant to the bromine-series flame retardant of the flame retardant is 29.
Wherein, the stabilizer comprises 75 percent by weight of one or the mixture of hydroxyethyl alkyl imidazoline, N-methyl pyrrolidone, N-dimethylacetamide, N-dimethylformamide or dimethyl sulfoxide;
the stabilizer also comprises one or a mixture of polyethylene glycol which is a hydrophilic polymer with the molecular weight of 18 ten thousand and polyvinylpyrrolidone which is a hydrophilic polymer with the molecular weight of K30-K50;
the stabilizer also comprises 4% of one or a mixture of phenylenediamine and dibutylamine;
the rest is 1, 2-ethylene glycol.
2) Stirring and mixing the polyurethane prepolymer 68, the antistatic complexing agent 11.25, the flame retardant 12 and the stabilizer 21 according to the weight ratio of the material prepared in the step 1) to prepare a gel medium;
3) Carrying out electrostatic spinning by using electrostatic spinning equipment;
4) Step 3), spinning is injected into the electrospinning solution by a spinning nozzle to form a film, the spinning voltage is 23KV, the feeding speed is 8 mu L/min, the receiving distance is 16cm, and the film forming temperature is 55 ℃;
5) Soaking the silk film obtained in the step 4) in a solution containing 2000ppm of sodium hypochlorite for 3.5 hours, and soaking the silk film in hot water at the temperature of 75 ℃ for 20 hours to obtain a finished product.
The electrospinning solution comprises 12% of polymer resin and 5% of additives dissolved in 83% of solvent according to weight ratio to prepare the spinning solution.
Wherein the polymer resin is at least one of polyacrylonitrile, polyvinylidene fluoride, cellulose acetate, polyvinyl chloride, polyester, polyamide, polypropylene, polysulfone or polyethersulfone; the solvent is at least one of water, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, acetone, tetrahydrofuran or acetic acid; the additive is at least one of polyethylene glycol, polyvinylpyrrolidone, potassium chloride, calcium chloride, sodium chloride, lithium bromide or lithium nitrate.
EXAMPLE III
Referring to fig. 2, a method for preparing a chemically modified electrospun membrane comprises the following steps:
1) Preparing polyurethane prepolymer, antistatic complexing agent, flame retardant and stabilizer respectively according to the proportion;
the polyurethane prepolymer comprises polyol and isocyanate, the antistatic complexing agent comprises a conjugated polymer material and a metal fiber material, and the flame retardant comprises chlorine flame retardant and bromine flame retardant.
Wherein the polyhydric alcohol comprises one or any combination mixture of ethylene glycol, 1, 4-butanediol, tetramethyl ether glycol and polyethylene glycol;
the isocyanate is 4,4' -diphenylmethane, diisocyanate or benzene diisocyanate;
the polyurethane prepolymer is prepared by mixing polyol and isocyanate, wherein the weight ratio of the polyol to the isocyanate is 85,
one or any combination mixture of 1, 4-butanediol, 1, 3-propanediol or diazobicyclooctane is added into the polyurethane prepolymer.
The conjugated polymer material comprises one or any combination mixture of polyaniline, polyacetylene, polypyridine, poly-p-phenylene, polythiophene, polyquinoline and poly-p-phenylene sulfide, and also comprises polypyrrole, wherein the weight of the polypyrrole of the conjugated polymer material is 45%;
the metal fiber material is lithium oxide fiber and polyethylene glycol/methacrylic acid copolymer particles with the weight ratio of 15;
the weight ratio of the conjugated polymer material to the metal fiber material of the antistatic complexing agent is 1.
Wherein the chlorine series flame retardant comprises one or any combination mixture of chlorinated polyethylene, tetrachlorophthalic anhydride, tetrachlorobisphenol A and hexachlorocyclopentadiene;
one or any combination mixture of brominated flame-retardant decabromodiphenyl ether, tetrabromophthalic, tetrabromobisphenol A and bromophthalic anhydride;
the flame retardant also comprises magnesium hydroxide and aluminum hydroxide, wherein the weight ratio of the magnesium hydroxide to the aluminum hydroxide is 6;
the weight ratio of the chlorine-series flame retardant to the bromine-series flame retardant of the flame retardant is 32.
Wherein the stabilizer comprises 90 wt% of one or a mixture of hydroxyethyl alkyl imidazoline, N-methyl pyrrolidone, N-dimethylacetamide, N-dimethylformamide or dimethyl sulfoxide;
the stabilizer also comprises one or a mixture of hydrophilic polymer polyethylene glycol with molecular weight of 30 ten thousand or hydrophilic polymer polyvinylpyrrolidone with K30-K50;
the stabilizer also comprises 6% of one or the mixture of phenylenediamine and dibutylamine;
the rest is 1, 2-ethylene glycol.
2) Stirring and mixing the polyurethane prepolymer 92, the antistatic complexing agent 22, the flame retardant 18 and the stabilizer 24 according to the weight ratio of the material prepared in the step 1) to prepare a gel medium;
3) Carrying out electrostatic spinning by using electrostatic spinning equipment;
4) Step 3) spinning yarns are injected into the electrospinning solution by a spinning nozzle to form a film, the spinning voltage is 35KV, the feeding speed is 15 mu L/min, the receiving distance is 30cm, and the film forming temperature is 60 ℃;
5) Soaking the silk film obtained in the step 4) in a solution containing 2200ppm of sodium hypochlorite for 4 hours, and then soaking the silk film in hot water at 90 ℃ for 25 hours to obtain a finished product.
The electrospinning solution comprises 20% of polymer resin and 10% of additives dissolved in 70% of solvent according to weight ratio to prepare the spinning solution.
Wherein the polymer resin is at least one of polyacrylonitrile, polyvinylidene fluoride, cellulose acetate, polyvinyl chloride, polyester, polyamide, polypropylene, polysulfone or polyethersulfone; the solvent is at least one of water, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, acetone, tetrahydrofuran or acetic acid; the additive is at least one of polyethylene glycol, polyvinylpyrrolidone, potassium chloride, calcium chloride, sodium chloride, lithium bromide or lithium nitrate.
The IR spectra of example 3 and comparative example (conventional spun film) are shown in FIG. 2, and it can be seen that the modified IR spectrum is at 3400cm -1 And 1000cm -1 Has a weaker vibration peak at 1750cm -1 A new peak appears nearby. The modifier is illustrated by reacting with hydroxyl groups on the polyurethane and introducing carbonyl groups.
TABLE 1 example and comparative example test data
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A chemically modified electrospun membrane comprising as major components:
65-92 parts of polyurethane prepolymer;
0.25 to 22 portions of antistatic complexing agent;
6 to 18 portions of flame retardant;
18-24 parts of a stabilizer;
the polyurethane prepolymer comprises polyalcohol and isocyanate, the antistatic complexing agent comprises conjugated polymer materials and metal fiber materials, and the flame retardant comprises chlorine flame retardants and bromine flame retardants.
2. A chemically modified electrospun membrane according to claim 1 wherein: the polyhydric alcohol comprises one or any combination mixture of ethylene glycol, 1, 4-butanediol, tetramethyl ether glycol and polyethylene glycol;
the isocyanate is 4,4' -diphenylmethane, diisocyanate or phenyl diisocyanate;
the polyurethane prepolymer is prepared by mixing polyol and isocyanate, wherein the weight ratio of the polyol to the isocyanate is 65-85,
the polyurethane prepolymer is added with one or any combination mixture of 1, 4-butanediol, 1, 3-propanediol or diazobicyclooctane.
3. A chemically modified electrospun membrane according to claim 1 wherein: the conjugated polymer material comprises one or any combination mixture of polyaniline, polyacetylene, polypyridine, poly-p-phenylene, polythiophene, polyquinoline and poly-p-phenylene sulfide, and also comprises polypyrrole, wherein the weight of the polypyrrole of the conjugated polymer material is 35-45%;
the metal fiber material is lithium oxide fiber and polyethylene glycol/methacrylic acid copolymer particles with the weight ratio of 5-15;
the weight ratio of the conjugated polymer material to the metal fiber material of the antistatic complexing agent is 1.
4. A chemically modified electrospun membrane according to claim 1 wherein: the chlorine series flame retardant comprises one or any combination mixture of chlorinated polyethylene, tetrachlorophthalic anhydride, tetrachlorobisphenol A and hexachlorocyclopentadiene;
one or any combination mixture of brominated flame-retardant decabromodiphenyl ether, tetrabromophthalic, tetrabromobisphenol A and bromophthalic anhydride;
the flame retardant also comprises magnesium hydroxide and aluminum hydroxide, wherein the weight ratio of the magnesium hydroxide to the aluminum hydroxide is 2-6;
the weight ratio of chlorine-series flame retardant to bromine-series flame retardant of the flame retardant is 26-32.
5. A chemically modified electrospun membrane according to claim 1 wherein: the stabilizer comprises 60 to 90 weight percent of one or the mixture of hydroxyethyl alkyl imidazoline, N-methyl pyrrolidone, N-dimethylacetamide, N-dimethylformamide or dimethyl sulfoxide;
the stabilizer also comprises one or a mixture of hydrophilic polymer polyethylene glycol with molecular weight of 5-30 ten thousand or hydrophilic polymer polyvinylpyrrolidone with K30-K50;
the stabilizer also comprises 2 to 6 percent of one of phenylenediamine or dibutylamine or the mixture thereof;
the rest is 1, 2-ethylene glycol.
6. A method of preparing a chemically modified electrospun membrane according to claim 1 comprising the steps of:
1) Preparing polyurethane prepolymer, antistatic complexing agent, flame retardant and stabilizer respectively according to the proportion;
2) Stirring and mixing 65-92 parts of polyurethane prepolymer, 0.25-22 parts of antistatic complexing agent, 6-18 parts of flame retardant and 18-24 parts of stabilizer according to the weight ratio of the material prepared in the step 1) to prepare a gel medium;
3) Carrying out electrostatic spinning by using electrostatic spinning equipment;
4) Step 3) spinning nozzles inject spinning into the electrospinning solution to form a film, the spinning voltage is 10-35 KV, the feeding speed is 1-15 mu L/min, the receiving distance is 2-30 cm, and the film forming temperature is 50-60 ℃;
5) Soaking the silk film obtained in the step 4) in a solution containing 1800-2200 ppm of sodium hypochlorite for 3-4 hours, and soaking the silk film in hot water at the temperature of 60-90 ℃ for 15-25 hours to obtain a finished product.
7. The method of preparing a chemically modified electrospun membrane according to claim 6, characterized in that: the electrospinning solution comprises 5-20% of polymer resin and 0-10% of additive by weight percent, which are dissolved in 70-95% of solvent to prepare spinning solution, and the sum of the components is 100%.
8. The method for preparing a chemically modified electrospun membrane according to claim 7, characterized in that: the polymer resin is at least one of polyacrylonitrile, polyvinylidene fluoride, cellulose acetate, polyvinyl chloride, polyester, polyamide, polypropylene, polysulfone or polyether sulfone; the solvent is at least one of water, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, acetone, tetrahydrofuran or acetic acid; the additive is at least one of polyethylene glycol, polyvinylpyrrolidone, potassium chloride, calcium chloride, sodium chloride, lithium bromide or lithium nitrate.
Priority Applications (1)
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| CN101306329A (en) * | 2007-05-17 | 2008-11-19 | 深圳市龙澄高科技环保有限公司 | Preparation method of polyurethane hollow fiber filter membrane |
| CN104532367A (en) * | 2014-12-19 | 2015-04-22 | 青岛大学 | Method for manufacturing polyurethane micro-nanofibers through solvent-free electrostatic spinning |
| CN106884209A (en) * | 2017-03-31 | 2017-06-23 | 青岛阳光动力生物医药技术有限公司 | A kind of antibacterial nano fiber or master batch |
| CN109504246A (en) * | 2018-11-28 | 2019-03-22 | 安徽安铝铝业有限公司 | Antistatic aluminium alloy extrusions and its preparation process |
| CN109957222A (en) * | 2019-03-28 | 2019-07-02 | 杭州本松新材料技术股份有限公司 | A kind of low precipitation flame retardant PBT composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101306329A (en) * | 2007-05-17 | 2008-11-19 | 深圳市龙澄高科技环保有限公司 | Preparation method of polyurethane hollow fiber filter membrane |
| CN104532367A (en) * | 2014-12-19 | 2015-04-22 | 青岛大学 | Method for manufacturing polyurethane micro-nanofibers through solvent-free electrostatic spinning |
| CN106884209A (en) * | 2017-03-31 | 2017-06-23 | 青岛阳光动力生物医药技术有限公司 | A kind of antibacterial nano fiber or master batch |
| CN109504246A (en) * | 2018-11-28 | 2019-03-22 | 安徽安铝铝业有限公司 | Antistatic aluminium alloy extrusions and its preparation process |
| CN109957222A (en) * | 2019-03-28 | 2019-07-02 | 杭州本松新材料技术股份有限公司 | A kind of low precipitation flame retardant PBT composition |
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