CN113529281B - Graphene/polysiloxane spinning fiber membrane and preparation method thereof - Google Patents
Graphene/polysiloxane spinning fiber membrane and preparation method thereof Download PDFInfo
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- 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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- 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
- D01D5/0053—Electro-spinning characterised by the initial state of the material the material being a low molecular weight compound or an oligomer, and the fibres being formed by self-assembly
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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
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
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- 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
- D04H1/4209—Inorganic fibres
- D04H1/4242—Carbon fibres
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- 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
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Abstract
The invention provides a graphene/polysiloxane spinning fiber membrane and a preparation method thereof. The preparation method comprises the following steps: dispersing graphene in a silane dilute solution, and stirring to react to obtain a graphene turbid liquid; uniformly mixing the graphene turbid liquid with a multifunctional silane monomer, adding a catalyst, and performing hydrolysis pre-polycondensation reaction and reduced pressure to remove small molecules to obtain a prepolymer; dissolving the prepolymer in an organic solvent to prepare a polymer spinning solution; and (3) carrying out electrostatic spinning to obtain the composite material. According to the invention, the condensation degree, the crosslinking degree and the structure of the polysiloxane prepolymer for spinning are regulated, the polysiloxane sol-gel chemical process in a short time of electrostatic spinning is accurately controlled, and the graphene is used for supporting and enhancing the fiber performance, so that the graphene/polysiloxane spinning fiber membrane is prepared, and the technical difficulty of curing and molding of polysiloxane spinning fibers is solved. The fiber membrane prepared by the invention has important application prospects in the fields of electrochemistry, catalysis, sensors, adsorption and separation, flexible electronic elements and medical engineering.
Description
Technical Field
The invention relates to a graphene/polysiloxane spinning fiber membrane and a preparation method thereof, belonging to the technical field of new materials.
Background
The high molecular polymer is spun into fiber with good mechanical property, and the fiber requires that the polymer is linear polymer with proper relative molecular mass, and the molecular chains of the polymer have enough valence force and good crystallization capability, such as polyethylene terephthalate, polycaprolactam, polyhexamethylene adipamide, polyparaphenylene terephthalamide, polyacrylonitrile, polypyrrolidone and the like. The polysiloxane is a polymer with Si-O-Si as a main chain structure and silicon atoms containing one or two organic groups, and has the characteristics of high and low temperature resistance, weather resistance, hydrolytic stability, biocompatibility and the like. Chinese patent document CN104805598A discloses a preparation method of a vinyl polysiloxane nanofiber membrane. The preparation process of the invention comprises the following steps: firstly, dissolving vinyl polysiloxane to prepare a spinning solution, adding electrolyte sodium chloride, carrying out electrostatic spinning by using an electrostatic spinning machine, then soaking the obtained vinyl polysiloxane nanofiber membrane in deionized water, and finally drying to obtain the vinyl polysiloxane ultrafine fiber membrane. The invention does not specify the molecular structure of the vinyl polysiloxane material, if the polymer is linear polysiloxane and the weight average molecular weight is 5000-180000g/mol, the polymer is fluid or high viscous fluid, and the electrostatic spinning can not obtain a formed fiber membrane structure; in the case of crosslinked vinyl polysiloxane, the method of the present invention cannot produce a good spinning solution, and thus a fiber membrane having good properties such as morphology cannot be obtained.
The linear polysiloxane is usually viscous fluid, has small valence force among high molecular chains and low crystallinity, and is not easy to prepare fibers with good mechanical properties by a traditional method; however, since a good spinning solution cannot be obtained in general, a fiber membrane having good properties such as morphology cannot be obtained by the electrospinning method. In view of the excellent performance of polysiloxane, if the polysiloxane fiber membrane with a micro-nano structure is prepared, the polysiloxane fiber membrane can be used as a separation membrane, an air filtration membrane, a catalytic carrier, a sound absorption material and the like used in high and low temperature environments, and can also be used as a biological material such as a tissue engineering scaffold and the like, so that the research on how to prepare the polysiloxane into a spinning fiber membrane with a non-woven fabric structure has important significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a graphene/polysiloxane spinning fiber membrane and a preparation method thereof. According to the invention, a multifunctional silane monomer and oxidized graphene are used as raw materials, a prepolymer with a specific crosslinking degree, structure and polycondensation degree is prepared through hydrolysis pre-polycondensation reaction, an electrostatic spinning method is adopted, a polysiloxane sol-gel chemical process in electrostatic spinning is accurately controlled within a short time, and a graphene reinforced fiber function is assisted, so that the graphene/polysiloxane spinning fiber membrane is prepared, and the technical difficulty of curing and forming polysiloxane spinning fiber is solved. The fiber membrane prepared by the invention has important application prospects in the fields of electrochemistry, catalysis, sensors, adsorption and separation, flexible electronic elements and medical engineering.
Description of terms:
graphene: the graphene of the invention refers to oxidized graphene.
The technical scheme of the invention is as follows:
a graphene/polysiloxane spinning fiber membrane, consisting of graphene/polysiloxane micro-or nanofibers; the diameter of the graphene/polysiloxane nano-fiber is 0.5-10 μm.
Preferably according to the invention, the fibrous membrane comprises graphene and polysiloxane; polysiloxane is a polymer with a cross-linked structure and is polymerized by a multifunctional silane monomer; the multifunctional silane monomer has a structural formula of R n SiY m Wherein, R is methyl, ethyl, propyl, phenyl, vinyl, aminopropyl, glycidoxypropyl, mercaptopropyl, or chloropropyl, Y is methoxy, ethoxy, or a chlorine atom, and n =1 or 2,m =4-n; the graphene content in the fiber membrane is 0.5-20.0 wt%; the graphene is a nanosheet with a thickness of 1.0-5.0 nm.
The preparation method of the graphene/polysiloxane spinning fiber membrane comprises the following steps:
(1) Fully dispersing graphene in a silane dilute solution, and then stirring to react to obtain a stable graphene turbid liquid;
(2) Uniformly mixing the graphene turbid liquid and a multifunctional silane monomer, adding a catalyst, and performing hydrolysis pre-polycondensation reaction and reduced pressure removal of small molecules to obtain a polysiloxane prepolymer containing graphene;
(3) Dissolving polysiloxane prepolymer containing graphene in an organic solvent to prepare a polymer spinning solution; and (3) carrying out electrostatic spinning to obtain the graphene/polysiloxane spinning fiber membrane.
According to the invention, in the step (1), the graphene is prepared by the conventional Hummers method and ultrasonic stripping method.
Preferably, in step (1), the silane is one or two of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane or dimethyldiethoxysilane.
Preferably, in step (1), the silane dilute solution is prepared by dissolving silane in an organic solvent; the organic solvent is tetrahydrofuran or toluene, and the concentration of the silane dilute solution is 2-50 mg/mL.
According to the invention, in the step (1), the stirring reaction temperature is 40-90 ℃, and the stirring reaction time is 12.0-30.0 h.
According to the invention, in the step (1), the concentration of graphene in the graphene suspension is preferably 0.2-1.0 g/mL.
According to the invention, in the step (1), the graphene in the suspension is graphene oxide with silane grafted on the surface, the chemically modified graphene has a sheet shape in a microscopic morphology, the thickness is 1.0-6.0 nm, and the width of the graphene sheet is 2.0-4.0 μm; the chemically modified graphene sheet contains a silane component.
Preferably, in step (2), the multifunctional silane monomer has the formula R n SiY m Wherein R is methyl, ethyl, propyl, phenyl, vinyl, aminopropyl, glycidoxypropyl, mercaptopropyl or chloropropyl, Y is a methoxy group, an ethoxy group or a chlorine atom, and n =1 or 2,m =4-n.
Preferably, the polyfunctional silane monomer is a trifunctional silane monomer R 1 SiY 3 And a difunctional silane monomer R 2 R 3 SiY 2 A combination of (1); wherein Y is a methoxy group, an ethoxy group and a chlorine atom; r 1 、R 2 、R 3 Each independently selected from methyl, ethyl, propyl, phenyl, vinyl, chloropropyl, aminopropyl, mercaptopropyl, or glycidyloxypropyl.
Further preferably, the trifunctional silane monomer is one or a combination of two or more of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-chloropropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane.
More preferably, the difunctional silane monomer is one or a combination of two or more of dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, gamma-chloropropylmethyldimethoxysilane, gamma-chloropropylmethyldiethoxysilane, gamma-aminopropylmethyldiethoxysilane and gamma-mercaptopropylmethyldiethoxysilane.
Further preferred, trifunctional silane monomers R 1 SiY 3 And a difunctional silane monomer R 2 R 3 SiY 2 1 to 20; preferably 1 to 15.
According to the present invention, in the step (2), the weight percentage of the graphene in the graphene suspension to the multifunctional silane monomer is preferably 0.5 to 20.0wt%, and more preferably 2.0 to 15.0wt%.
According to the invention, in the step (2), the catalyst is an aqueous solution of an acid catalyst, the acid catalyst is acetic acid, hydrochloric acid or sulfuric acid, and the mass concentration of the aqueous solution of the acid catalyst is 5.0-20.0 wt%; the pH of the system was controlled by adding catalyst = 2-5.
According to the invention, in the step (2), the temperature of the hydrolysis pre-polycondensation reaction is 30-90 ℃, preferably 50-80 ℃; the hydrolysis pre-polycondensation reaction time is 4 to 24 hours, preferably 5 to 12 hours.
According to the invention, in step (2), the conditions for removing the small molecules under reduced pressure are as follows: the vacuum degree is 10mmHg, the temperature is 90-150 ℃, and the time for removing the micromolecules under reduced pressure is 0.5-2.0 h.
Preferably, in step (3), the organic solvent is one or a mixture of two or more of tetrahydrofuran, dichloromethane, ethanol, isopropanol, toluene, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide; the concentration of the prepolymer containing the graphene polysiloxane in the polymer spinning solution is 0.2-2.0 g/mL.
Preferably, according to the present invention, in the step (3), the electrospinning conditions are: the electrostatic spinning voltage is 15-25 kV, the receiving distance is more than 20.0cm, the diameter of the nozzle of the spinneret is 0.5-2.0 mm, and the flow rate of the spinning solution is 0.5-5.0 mL/h; preferably, the receiving distance is 25.0-30.0 cm, and the flow rate of the spinning solution is 1.5-4.5 mL/h.
The invention has the following technical characteristics and beneficial effects:
(1) According to the invention, silane is firstly used for carrying out chemical modification on the surface of graphene, and a chemical modification layer is formed on the surface of graphene, so that the compatibility of graphene and polysiloxane is increased, the graphene sheet is easily dispersed in polysiloxane matrix polymer, and a fiber membrane with good fiber morphology is obtained; at the same time, chemical reactivity with the polysiloxane prepolymer is provided. Due to the addition of the graphene, on one hand, the obtained fiber membrane is endowed with functionality; on the other hand, the fiber membrane plays a role in supporting and reinforcing fibers, thereby being beneficial to obtaining the fiber membrane with good fiber form.
(2) In the electrostatic spinning process, proper conditions such as spinning voltage, spinning receiving distance and spinning solution flow rate are selected, rapid solvent volatilization and polysiloxane sol-gel chemical transformation synchronously occur in the spinning process, the polysiloxane sol-gel chemical process in the short time of electrostatic spinning is accurately controlled by regulating and controlling the condensation degree, crosslinking degree and structure of polysiloxane prepolymer for spinning, and the fiber performance is supported and enhanced by graphene, so that the technical difficulty of curing and forming of polysiloxane spinning fibers is solved, and a good polysiloxane spinning fiber film is obtained.
(3) The preparation method of the fiber membrane is simple, the reaction condition is mild, and the cost is low; the obtained fiber membrane has controllable pore size and good fiber shape, and has important application prospect in the fields of electrochemistry, catalysis, sensors, adsorption and separation, flexible electronic elements and medical engineering.
Drawings
Fig. 1 is a scanning electron microscope image of the graphene/polysiloxane spinning fiber film prepared in example 1.
Fig. 2 is a scanning electron microscope image of the graphene/polysiloxane spinning fiber film prepared in example 1.
Fig. 3 is a scanning electron micrograph of the graphene/polysiloxane spun fiber membrane prepared in comparative example 1.
Detailed Description
The present invention will be further described with reference to the following examples, but is not limited thereto. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Also, the experimental procedures described in the following examples are all conventional procedures unless otherwise specified, and the reagents and materials described therein are commercially available without otherwise specified.
In the embodiment, the graphene is prepared by the existing Hummers method and ultrasonic peeling method. The prepared graphene is a nanosheet with the thickness of 1.0-5.0 nm.
Example 1
A preparation method of a graphene/polysiloxane spinning fiber membrane comprises the following steps:
adding 5.0g of graphene into 10.0mL of tetrahydrofuran solution of methyltrimethoxysilane with the concentration of 5mg/mL, uniformly mixing by ultrasonic dispersion, and then stirring and reacting at 50 ℃ for 24.0h to obtain graphene suspension; and (2) uniformly mixing 160.0g of methyltriethoxysilane and 10.0g of dimethyldiethoxysilane, adding the prepared graphene oxide suspension, performing ultrasonic dispersion, stirring to form a uniform dispersion liquid, and adding a dilute hydrochloric acid aqueous solution with the weight percentage concentration of 10.0wt% until the pH of the reactant system is =3.0. Reacting at 80 deg.C for 6h, and removing low molecular weight under reduced pressure at 90 deg.C under vacuum degree of 10mmHg for 1.0h to obtain polysiloxane prepolymer (liquid resin); the control of the polycondensation degree is realized by controlling the polycondensation reaction conditions and the reduced pressure removal of low molecular weight. Tetrahydrofuran is used as a solvent, and the prepolymer is prepared into a prepolymer spinning solution with the concentration of 0.8 g/mL. And spinning under the conditions that the diameter of a spinneret orifice is 0.9mm, the electrostatic spinning voltage is 15kV, the receiving distance is 30cm, and the flow rate of a spinning solution is 1.5mL/h to obtain the graphene/polysiloxane spinning fiber membrane.
Fig. 1 and fig. 2 are scanning electron micrographs of the graphene/polysiloxane spinning fiber film prepared in this example, and it can be seen from the graphs that the fiber diameter is 3.0 to 5.0 μm.
Example 2
A preparation method of a graphene/polysiloxane spinning fiber membrane comprises the following steps:
adding 35.0g of graphene into 40.0mL of phenyltrimethoxysilane toluene solution with the concentration of 15mg/mL, performing ultrasonic dispersion and uniform mixing, and then stirring and reacting at 60 ℃ for 30.0h to obtain graphene suspension. Uniformly mixing 140.0g of phenyltrimethoxysilane and 100.5g of gamma-mercaptopropylmethyldiethoxysilane, adding the prepared graphene oxide suspension, performing ultrasonic dispersion, rapidly stirring to form uniform dispersion, and adding a dilute hydrochloric acid aqueous solution with the weight percentage concentration of 10.0wt% until the pH of the reactant system is =2.0. The reaction was carried out at 60 ℃ for 12.0 hours, and then the low molecular weight was removed under reduced pressure at 110 ℃ under a vacuum of 10mmHg for 1.2 hours to obtain a polysiloxane prepolymer (liquid resin). Toluene is used as a solvent, and the prepolymer is prepared into a prepolymer spinning solution with the concentration of 1.0g/mL. Spinning under the conditions that the diameter of a spinneret orifice is 0.8mm, the electrostatic spinning voltage is 20kV, the receiving distance is 30.0cm and the flow rate of a spinning solution is 2.0mL/h to obtain the graphene/polysiloxane spinning fiber membrane, wherein the fiber diameter is 2.0-4.0 mu m.
Experimental example 3
A preparation method of a graphene/polysiloxane spinning fiber membrane comprises the following steps:
adding 15.0g of graphene into 20.0mL of methyltriethoxysilane tetrahydrofuran solution with the concentration of 10mg/mL, performing ultrasonic dispersion and uniform mixing, and then stirring and reacting at 40 ℃ for 30.0h to obtain graphene suspension. Uniformly mixing 105.0g of methyltrimethoxysilane and 50.0g of gamma-chloropropylmethyldiethoxysilane, adding the prepared graphene oxide suspension, performing ultrasonic dispersion, rapidly stirring to form a uniform dispersion liquid, and adding a dilute hydrochloric acid aqueous solution with the weight percentage concentration of 10.0wt% until the pH of the reactant system is =4.0. The reaction was carried out at 50 ℃ for 8.0 hours, and then the low molecular weight was removed under reduced pressure at 95 ℃ under a vacuum of 10mmHg for 1.5 hours to obtain a polysiloxane prepolymer (liquid resin). Tetrahydrofuran is used as a solvent, and the prepolymer is prepared into a prepolymer spinning solution with the concentration of 0.30 g/mL. Spinning under the conditions that the diameter of a spinneret orifice is 1.2mm, the electrostatic spinning voltage is 15kV, the receiving distance is 25.0cm and the flow rate of a spinning solution is 3.0mL/h to obtain the graphene/polysiloxane spinning fiber membrane, wherein the fiber diameter is 4.0-6.0 mu m.
Experimental example 4
A preparation method of a graphene/polysiloxane spinning fiber membrane comprises the following steps:
adding 10.0g of graphene into 20.0mL of vinyltrimethoxysilane toluene solution with the concentration of 8mg/mL, performing ultrasonic dispersion and uniform mixing, and then stirring and reacting at 80 ℃ for 20.0h to obtain graphene suspension. 150.0g of methyltrimethoxysilane, 10.0g of vinyltrimethoxysilane and 18.7g of methylphenyldiethoxysilane are mixed uniformly, 10.0mL of the graphene oxide suspension prepared above is added, ultrasonic dispersion is carried out, rapid stirring is carried out until a uniform dispersion liquid is formed, and an acetic acid aqueous solution with the weight percentage concentration of 15.0wt% is added until the pH of the reactant system is =3.5. The reaction was carried out at 50 ℃ for 10 hours, and then the low molecular weight was removed under reduced pressure at 90 ℃ under a vacuum of 10mmHg for 0.5 hour to give a polysiloxane prepolymer (liquid resin). Toluene is used as a solvent, and the prepolymer is prepared into a polymer spinning solution with the concentration of 0.5 g/mL. Spinning under the conditions that the diameter of a spinneret orifice is 0.7mm, the voltage under electrostatic spinning conditions is 20kV, the receiving distance is 30.0cm and the flow rate of a spinning solution is 4.5mL/h to obtain the graphene/polysiloxane spinning fiber membrane, wherein the fiber diameter is 1.0-3.0 mu m.
Experimental example 5
A preparation method of a graphene/polysiloxane spinning fiber membrane comprises the following steps:
adding 12.0g of graphene into 25.0mL of 10mg/mL dimethyldiethoxysilane tetrahydrofuran solution, performing ultrasonic dispersion and uniform mixing, and then stirring and reacting at 50 ℃ for 24.0h to obtain a graphene suspension. Uniformly mixing 200.0g of gamma-glycidoxypropyltrimethoxysilane and 10.0g of dimethyldiethoxysilane, adding the prepared graphene oxide suspension, performing ultrasonic dispersion, and rapidly stirring to form uniform dispersion liquid. An aqueous acetic acid solution at a weight percent concentration of 15.0wt% was added to the reactant system pH =5.0. The reaction was carried out at 70 ℃ for 5 hours, and then the low molecular weight was removed under reduced pressure at 120 ℃ under a vacuum of 10mmHg for 2.0 hours to give a polysiloxane prepolymer (liquid resin). tetrahydrofuran/N, N-dimethylformamide (volume ratio of 5/1) is used as a solvent, the prepolymer is prepared into a polymer spinning solution with the concentration of 0.2g/mL, and the graphene/polysiloxane spinning fiber membrane is obtained by spinning under the conditions that the diameter of a spinneret orifice is 0.5mm, the voltage of electrostatic spinning condition is 25kV, the receiving distance is 25.0cm and the flow rate of the spinning solution is 2.0mL/h, wherein the fiber diameter is 0.7-2.0 mu m.
Comparative example 1
A preparation method of a graphene/polysiloxane spinning fiber membrane comprises the following steps:
adding 5.0g of graphene into 10.0mL of 5 mg/mL-methyltrimethoxysilane tetrahydrofuran solution, performing ultrasonic dispersion and uniform mixing, and then stirring and reacting at 50 ℃ for 24.0h to obtain a graphene suspension; uniformly mixing 10.0g of methyltriethoxysilane and 160.0g of dimethyldiethoxysilane, adding the prepared graphene oxide suspension, performing ultrasonic dispersion, stirring to form uniform dispersion liquid, and adding a dilute hydrochloric acid aqueous solution with the weight percentage concentration of 10.0wt% until the pH of a reactant system is =3.0. Reacted at 80 ℃ for 6 hours, and then the low molecular weight was removed under reduced pressure at 90 ℃ under a vacuum of 10mmHg for 1.0 hour to give a polysiloxane prepolymer (liquid resin). Tetrahydrofuran is used as solvent, and the prepolymer is prepared into a prepolymer spinning solution with the concentration of 0.8 g/mL. Spinning under the conditions that the diameter of a spinneret orifice is 0.9mm, the electrostatic spinning voltage is 15kV, the receiving distance is 30.0cm and the flow rate of a spinning solution is 1.5mL/h to obtain the graphene/polysiloxane spinning fiber membrane.
Fig. 3 is a scanning electron microscope image of the graphene/polysiloxane spinning fiber film prepared in the comparative example, and it can be seen from the image that the spinning fiber film with the adhesion structure is obtained by using the same electrostatic spinning process and conditions under the condition that the polysiloxane molecular crosslinking structure and the prepolymer polycondensation degree are not controlled well.
Claims (7)
1. A preparation method of a graphene/polysiloxane spinning fiber membrane, wherein the fiber membrane consists of graphene/polysiloxane fibers; the diameter of the graphene/polysiloxane fiber is 0.7 to 6 mu m; polysiloxane is a polymer with a cross-linked structure and is polymerized by a multifunctional silane monomer; the content of graphene in the fiber membrane is 0.5 to 20.0wt%; the graphene is a nanosheet with the thickness of 1.0 to 5.0 nm;
the preparation method comprises the following steps:
(1) Fully dispersing graphene in a silane dilute solution, and then stirring to react to obtain a stable graphene turbid liquid;
the silane is one or two of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane or dimethyldiethoxysilane; the silane dilute solution is prepared by dissolving silane in an organic solvent; the organic solvent is tetrahydrofuran or toluene, and the concentration of the silane dilute solution is 2 to 50 mg/mL; the stirring reaction temperature is 40 to 90 ℃, and the stirring reaction time is 12.0 to 30.0 hours; the concentration of graphene in the graphene turbid liquid is 0.2-1g/mL;
(2) Uniformly mixing the graphene turbid liquid and a multifunctional silane monomer, adding a catalyst, and performing hydrolysis pre-polycondensation reaction and reduced pressure removal of small molecules to obtain a polysiloxane prepolymer containing graphene;
the polyfunctional silane monomer is a trifunctional silane monomer R 1 SiY 3 And a difunctional silane monomer R 2 R 3 SiY 2 A combination of (1); wherein Y is methoxy, ethoxy and chlorine atom; r is 1 、R 2 、R 3 Each independently selected from methyl, ethyl, propyl, phenyl, vinyl, chloropropyl, aminopropyl, mercaptopropyl, or glycidyloxypropyl; trifunctional silane monomers R 1 SiY 3 And a difunctional silane monomer R 2 R 3 SiY 2 The molar ratio of (a) to (b) is 1 to 20; the weight percentage of graphene in the graphene suspension in the multifunctional silane monomer is 0.5 to 20.0wt%; the catalyst is an aqueous solution of an acidic catalyst, the acidic catalyst is acetic acid, hydrochloric acid or sulfuric acid, and the mass concentration of the aqueous solution of the acidic catalyst is 5.0-20.0 wt%; controlling the pH of the system by adding a catalyst to be 2-5; the hydrolysis pre-polycondensation reaction temperature is 30 to 90 ℃; the hydrolysis pre-polycondensation reaction time is 4 to 24 hours; the conditions for removing the small molecules under reduced pressure are as follows: the vacuum degree is 10mmHg, the temperature is 90 to 150 ℃, and the time for removing the micromolecules under reduced pressure is 0.5 to 2.0 hours;
(3) Dissolving polysiloxane prepolymer containing graphene in an organic solvent to prepare a polymer spinning solution; obtaining a graphene/polysiloxane spinning fiber membrane through electrostatic spinning; the electrostatic spinning conditions are as follows: the electrostatic spinning voltage is 15 to 25kV, the receiving distance is more than 20.0cm, the diameter of a spinneret orifice is 0.5 to 2.0mm, and the flow rate of a spinning solution is 0.5 to 5.0 mL/h.
2. The method for preparing the graphene/polysiloxane spinning fiber membrane according to claim 1, wherein the trifunctional silane monomer is one or more of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-chloropropyltriethoxysilane or gamma-glycidoxypropyltrimethoxysilane.
3. The method for preparing the graphene/polysiloxane spinning fiber film according to claim 1, wherein the difunctional silane monomer is one or a combination of two or more of dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, gamma-chloropropylmethyldimethoxysilane, gamma-chloropropylmethyldiethoxysilane, gamma-aminopropylmethyldiethoxysilane or gamma-mercaptopropylmethyldiethoxysilane.
4. The method for preparing the graphene/polysiloxane spinning fiber membrane according to claim 1, wherein the trifunctional silane monomer R 1 SiY 3 And a difunctional silane monomer R 2 R 3 SiY 2 The molar ratio of (b) is 1 to 15.
5. The method for preparing the graphene/polysiloxane spinning fiber membrane according to claim 1, wherein the step (2) comprises one or more of the following conditions:
i. the weight percentage of graphene in the graphene suspension in the multifunctional silane monomer is 2.0-15.0 wt%;
ii. The hydrolysis pre-polycondensation reaction temperature is 50 to 80 ℃; the hydrolysis pre-polycondensation reaction time is 5 to 12 hours.
6. The method for preparing the graphene/polysiloxane spinning fiber membrane according to claim 1, wherein in the step (3), the organic solvent is one or a mixture of two or more of tetrahydrofuran, dichloromethane, ethanol, isopropanol, toluene, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide; the concentration of the graphene polysiloxane prepolymer in the polymer spinning solution is 0.2 to 2.0g/mL.
7. The method for preparing the graphene/polysiloxane spinning fiber membrane according to claim 1, wherein in the step (3), the receiving distance is 25.0 to 30.0cm, and the flow rate of a spinning solution is 1.5 to 4.5mL/h.
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