CN109629032B - Preparation method of high-tensile-modulus polymer nano composite fiber based on electrostatic spinning technology - Google Patents
Preparation method of high-tensile-modulus polymer nano composite fiber based on electrostatic spinning technology Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/56—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
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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
- 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
- D01F6/92—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 polyesters
Abstract
The invention belongs to the technical field of electrostatic spinning, and particularly relates to a preparation method of a high-tensile-modulus polymer nano composite fiber based on an electrostatic spinning technology. The invention adopts the electrostatic spinning method to prepare the high-tensile modulus nanofiber, the operation is easy, the production process is simple, the requirement on equipment is low, the obtained nano composite fiber only improves the mechanical behavior of the original polymer fiber, and has small influence on other characteristics, the specific surface area of the fiber is large, the tensile modulus is high, and the industrialization is easy.
Description
Technical Field
The invention belongs to the technical field of electrostatic spinning, and particularly relates to a preparation method of a high-tensile-modulus polymer nano composite fiber based on an electrostatic spinning technology.
Background
The electrostatic spinning is a method for efficiently preparing polymer nano composite fibers or fiber felt materials, and functional materials prepared by the technology are widely applied to the fields of biomedical materials, electronic devices and the like. Electrospun fibers have diameters of about 0.05 to 2 microns, with smaller diameters generally resulting in a mechanical tensile modulus that is not high, limiting their utility. Common methods for mechanically modifying electrospun fibers include preparing very fine fibers (when the diameter is smaller than a certain size, such as 100nm, the increase in young's modulus is inversely proportional to the decrease in diameter), compounding with polymers or inorganic particles having a higher tensile modulus, and the like. The preparation of the superfine fiber has higher requirements on materials, equipment and processes, and poor universality, and the spinning strategy of compounding the polymer and the inorganic particles is widely adopted at present because of simple operation and obvious enhancement effect, and the process can realize high-quality complementation of the two substances, thereby greatly improving the material performance, particularly the mechanical property. At present, spherical nanoparticles, nanorods, nanotubes, nanosheets and the like made of various materials are generally adopted in the electrostatic spinning preparation process of polymer nano composite fibers, however, the particles are easy to agglomerate, and the dispersion and arrangement of the particles in a solvent or a polymer matrix are influenced, so that the final mechanical enhancement effect is limited. In addition, there are also related researches on adding a polymer system after surface modification of nanoparticles, promoting dispersion of particles and enhancing the interfacial bonding force between the particles and the polymer. In order to achieve the target reinforcing effect, the polymer nano composite fiber prepared by the method still has the problems of high filling amount and high processing requirement on nano particles. While nanoparticles with three-dimensional branching (such as quadrangular pyramid) will show great potential in the field of reinforced polymer nanocomposite fibers due to their own advantages in spatial dispersion.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, the present invention aims to provide a method for preparing a polymer nanocomposite fiber with high tensile modulus based on electrospinning, which is easy to handle, has low requirements for equipment, and can be obtained at a lower addition amount.
A preparation method of high tensile modulus polymer nano composite fiber based on electrostatic spinning technology is characterized by comprising the following steps:
1) preparing an electrospinning solution: dissolving a coupling agent in a water-ethanol mixed solution, performing ultrasonic dispersion for 1-3h at room temperature, adding quadrangular pyramid zinc oxide nano particles, heating and stirring for 0.5-4h, filtering, washing filter residues with deionized water, and performing vacuum drying to obtain modified nano zinc oxide particles; dispersing a polymer in an organic solvent to prepare a polymer solution, adding the modified nano zinc oxide particles prepared in the step (a) into the polymer solution, and fully stirring to obtain an electrospinning solution;
2) preparing high tensile modulus fiber: loading the electrospinning solution obtained in the step 1) into an injector, spinning at a propelling speed of 0.01-0.04mL/min, setting a positive voltage at 10-30KV, and collecting the fibers obtained by spinning on a rotating metal roller or a rotating sheet to obtain the high-tensile-modulus polymer nano composite fiber.
The preparation method of the high-tensile-modulus polymer nano composite fiber based on the electrostatic spinning technology is characterized in that in the step 1), the polymer is polystyrene, polyvinylidene fluoride, polylactic acid, polyimide, polyamide, polyvinyl alcohol, polyacrylonitrile or polypropylene.
The preparation method of the high-tensile-modulus polymer nano composite fiber based on the electrostatic spinning technology is characterized in that in the step 1), the coupling agent is a silane coupling agent or a titanate coupling agent;
the silane coupling agent is gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, vinyl triethoxysilane or vinyl tri (beta-methoxyethoxy) silane;
the titanate coupling agent is pyrophosphate titanate, isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate or isopropyl tri (dioctyl phosphate acyloxy) titanate.
The preparation method of the high-tensile-modulus polymer nano composite fiber based on the electrostatic spinning technology is characterized in that in the step 1), the average arm diameter of the quadrangular pyramid zinc oxide nano particles is controlled within 50nm, and the average arm length is controlled within 100 nm.
The preparation method of the high-tensile-modulus polymer nano composite fiber based on the electrostatic spinning technology is characterized in that in the step 1), the organic solvent is tetrahydrofuran or dimethylformamide.
The preparation method of the high-tensile-modulus polymer nano composite fiber based on the electrostatic spinning technology is characterized in that in the step 1) of the electrospinning solution, the mass concentration of the polymer is 5-30%.
The preparation method of the high-tensile-modulus polymer nano composite fiber based on the electrostatic spinning technology is characterized in that in the step 1) of the electrospinning solution, the mass concentration of the modified nano zinc oxide particles is 1-8%.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
the invention adopts the electrostatic spinning method to prepare the high-tensile modulus polymer nano composite fiber, has easy operation, simple production process and low requirement on equipment, and the obtained polymer nano composite fiber has high Young modulus, small nano particle filling amount and easy industrialization.
According to the invention, after the nano zinc oxide particles are modified by the coupling agent, the molecular chains of the coupling agent on the nano particles are entangled with the polymer chains, so that the interaction force between the nano particles and the polymer components is obviously enhanced, the nano particles are beneficial to the dispersion of the nano particles and the stress transfer between the nano particles and the polymer under the stress condition, and the tensile modulus of the polymer nano composite fiber is finally enhanced.
Drawings
FIG. 1a is a scanning electron micrograph of polypropylene composite fibers of a control system of example 3;
FIG. 1b is a scanning electron micrograph of polypropylene composite fibers of the experimental system of example 3;
FIG. 2a is a tensile test stress-strain curve of a polystyrene composite fiber of the experimental system of example 1;
FIG. 2b is a tensile test stress-strain curve of the polystyrene composite fiber of the experimental system of comparative example 1.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
Under nitrogen atmosphere, the zinc foil is placed in a quartz tube (120 cm long and 10 cm in diameter) at 700 ℃ and oxygen and saturated water vapor are slowly introduced at a rate of 50 standard milliliters per minute to participate in the reaction (the volume ratio of the oxygen to the saturated water vapor is 1: 1, namely the introduction rates of the oxygen and the saturated water vapor are both 25 standard milliliters per minute), the oxygen flow rate and the reaction time are strictly controlled, and quadrangular pyramid-shaped zinc oxide nanoparticles with narrow size distribution range, average arm diameter within about 25nm and average arm length of about 70nm are obtained.
Dissolving 2.0g of coupling agent (gamma-aminopropyltriethoxysilane) in 50mL of water-ethanol mixed solution (the volume ratio of water to ethanol is 1: 1), ultrasonically dispersing for 1h at room temperature, adding 0.8g of the synthesized quadrangular pyramid-shaped zinc oxide nanoparticles, heating and stirring for 2h at 60 ℃, filtering, washing filter residues with deionized water, and then drying in vacuum at 60 ℃ to obtain the modified nano zinc oxide particles.
Dispersing polystyrene (Mw = 350000) in tetrahydrofuran, preparing a polystyrene solution with the mass concentration of 15%, then adding the modified nano zinc oxide particles obtained by the preparation method, and fully stirring to obtain an electrospinning solution; in the electrospinning solution, the mass concentration of the modified nano zinc oxide particles is 3.5%.
And (3) filling the electrospinning solution into an injector, spinning at a propelling speed of 0.02mL/min with the positive voltage set to be 20KV, and collecting the fibers on a rotating metal roller to prepare the modified quadrangular pyramid zinc oxide nanoparticle-filled polystyrene composite fibers or a fiber felt formed by randomly stacking a large number of fibers. A fiber mat (thickness controlled to be about 0.05 mm) having a size of 0.8cm × 3.0cm was cut out, the cross-sectional area was estimated from the mass thereof, and the tensile modulus thereof was measured in a dynamic mechanical analyzer (average of 10 effective measurements). The tensile modulus was increased by 181% compared to the control system without nanoparticles, which is different from the experimental system for preparing modified tetrapod-like zinc oxide nanoparticles-filled polystyrene composite fiber in example 1 in that the modified tetrapod-like zinc oxide nanoparticles were not added to the electrospinning solution during the preparation process. The reason why the tensile modulus is significantly increased after the nanoparticles are added in this example is as follows: the nanoparticles themselves possess a significantly higher young's modulus than the polymer; the nanoparticles modified by the coupling agent have a large number of short chains with strong affinity with the polymer, and the short chains are mutually entangled with the polymer chains, so that the interaction force between the polymer and the nanoparticles is improved; in addition, the modified particles can be more uniformly dispersed in the polymer; in the case of stretching, the stress is transferred from the polymer to the nanoparticles and the tensile modulus of the composite fiber is significantly increased.
Example 2
Under nitrogen atmosphere, the zinc foil is placed in a quartz tube (120 cm long and 10 cm in diameter) at 700 ℃ and oxygen and saturated water vapor are slowly introduced at a rate of 50 standard milliliters per minute to participate in the reaction (the volume ratio of the oxygen to the saturated water vapor is 1: 1, namely the introduction rates of the oxygen and the saturated water vapor are both 25 standard milliliters per minute), the oxygen flow rate and the reaction time are strictly controlled, and quadrangular pyramid-shaped zinc oxide nanoparticles with narrow size distribution range, average arm diameter within about 25nm and average arm length of about 70nm are obtained.
Dissolving 2.0g of coupling agent (pyrophosphate titanate) in 50mL of water-ethanol solution (the volume ratio of water to ethanol is 1: 1), ultrasonically dispersing for 1h at room temperature, adding 0.8g of the synthesized quadrangular pyramid zinc oxide nanoparticles, heating and stirring for 2h at 60 ℃, filtering, washing filter residues with deionized water, and then drying in vacuum at 60 ℃ to obtain the modified nano zinc oxide particles.
Dispersing polyvinylidene fluoride (Mw = 250000) in tetrahydrofuran to prepare a polyvinylidene fluoride solution with the mass concentration of 15%, then adding the modified nano zinc oxide particles prepared in the step (a), and fully stirring to obtain an electrospinning solution; in the electrospinning solution, the mass concentration of the modified nano zinc oxide particles is 3.5%.
And (3) filling the electrospinning solution into an injector, spinning at the advancing speed of 0.02mL/min, setting the positive voltage at 20KV, and collecting the fibers on a rotating metal roller to prepare the polyvinylidene fluoride composite fibers filled with the modified quadrangular pyramid zinc oxide nanoparticles or the fiber felt formed by randomly stacking a large number of fibers. A fiber mat (thickness controlled to be about 0.05 mm) having a size of 0.8cm × 3.0cm was cut out, the cross-sectional area was estimated from the mass thereof, and the tensile modulus thereof was measured in a dynamic mechanical analyzer (average of 10 effective measurements). The tensile modulus is increased by 161% compared with the control system without nanoparticles, and the control system is different from the experimental system for preparing the polyvinylidene fluoride composite fiber filled with the modified quadrangular pyramid-shaped zinc oxide nanoparticles in example 2 in that the modified quadrangular pyramid-shaped zinc oxide nanoparticles are not added into the electrospinning solution in the preparation process.
Example 3
Under nitrogen atmosphere, the zinc foil is placed in a quartz tube (120 cm long and 10 cm in diameter) at 700 ℃ and oxygen and saturated water vapor are slowly introduced at a rate of 50 standard milliliters per minute to participate in the reaction (the volume ratio of the oxygen to the saturated water vapor is 1: 1, namely the introduction rates of the oxygen and the saturated water vapor are both 25 standard milliliters per minute), the oxygen flow rate and the reaction time are strictly controlled, and quadrangular pyramid-shaped zinc oxide nanoparticles with narrow size distribution range, average arm diameter within about 25nm and average arm length of about 70nm are obtained.
Dissolving 2.0g of coupling agent (gamma-aminopropyltriethoxysilane) in 50mL of water-ethanol solution, ultrasonically dispersing for 1h at room temperature, adding 0.8g of synthesized quadrangular pyramid zinc oxide nanoparticles, heating and stirring for 2h at 60 ℃, filtering, washing filter residues with deionized water, and then drying in vacuum at 60 ℃ to obtain the modified nano zinc oxide particles.
Dispersing polypropylene (Mw = 350000) in tetrahydrofuran to prepare a polypropylene solution with a mass concentration of 15%, adding the modified nano zinc oxide particles prepared above, and fully stirring to obtain an electrospinning solution; in the electrospinning solution, the mass concentration of the modified nano zinc oxide particles is 3.5%.
And (3) filling the electrospinning solution into an injector, spinning at a propelling speed of 0.02mL/min with the positive voltage set to be 20KV, and collecting the fibers on a rotating metal roller to prepare the polypropylene composite fibers filled with the modified quadrangular pyramid zinc oxide nanoparticles or the fiber felt formed by randomly stacking a large number of fibers. A fiber mat (thickness controlled to be about 0.05 mm) having a size of 0.8cm × 3.0cm was cut out, the cross-sectional area was estimated from the mass thereof, and the tensile modulus thereof was measured in a dynamic mechanical analyzer (average of 10 effective measurements). The tensile modulus is increased by 172% compared with a control system without nanoparticles, and the difference of the control system is that the modified quadrangular pyramid zinc oxide nanoparticles are not added in the electrospinning solution in the preparation process compared with the experimental system for preparing the modified quadrangular pyramid zinc oxide nanoparticle-filled polypropylene composite fiber in example 3.
Example 4
Under nitrogen atmosphere, the zinc foil is placed in a quartz tube (120 cm long and 10 cm in diameter) at 700 ℃ and oxygen and saturated water vapor are slowly introduced at a rate of 50 standard milliliters per minute to participate in the reaction (the volume ratio of the oxygen to the saturated water vapor is 1: 1, namely the introduction rates of the oxygen and the saturated water vapor are both 25 standard milliliters per minute), the oxygen flow rate and the reaction time are strictly controlled, and quadrangular pyramid-shaped zinc oxide nanoparticles with narrow size distribution range, average arm diameter within about 25nm and average arm length of about 70nm are obtained.
Dissolving 2.0g of coupling agent (gamma-aminopropyltriethoxysilane) in 50mL of water-ethanol solution, ultrasonically dispersing for 1h at room temperature, adding 0.8g of synthesized quadrangular pyramid zinc oxide nanoparticles, heating and stirring for 2h at 60 ℃, filtering, washing filter residues with deionized water, and then drying in vacuum at 60 ℃ to obtain the modified nano zinc oxide particles.
Dispersing polylactic acid (Mw = 250000) in tetrahydrofuran to prepare a polylactic acid solution with the mass concentration of 15%, then adding the modified nano zinc oxide particles prepared in the step (a), and fully stirring to obtain an electrospinning solution; in the electrospinning solution, the mass concentration of the modified nano zinc oxide particles is 3.5%.
And (3) filling the electrospinning solution into an injector, spinning at the advancing speed of 0.02mL/min, setting the positive voltage at 20KV, and collecting the fibers on a rotating metal roller to prepare the polylactic acid composite fibers filled with the modified quadrangular pyramid zinc oxide nanoparticles or the fiber felt formed by randomly stacking a large number of fibers. A fiber mat (thickness controlled to be about 0.05 mm) having a size of 0.8cm × 3.0cm was cut out, the cross-sectional area was estimated from the mass thereof, and the tensile modulus thereof was measured in a dynamic mechanical analyzer (average of 10 effective measurements). The tensile modulus is increased by 129% compared with a control system without the added nanoparticles, and the control system is different from the experimental system for preparing the polylactic acid composite fiber filled with the modified tetrapyramid-shaped zinc oxide nanoparticles in example 4 in that the modified tetrapyramid-shaped zinc oxide nanoparticles are not added into the electrospinning solution in the preparation process.
In examples 1 to 4, the polymer base materials were different, and the degree of improvement in tensile modulus was also different. Fig. 1a is an SEM image of a control system (polypropylene fiber without nanoparticles) prepared in example 3, and fig. 1b is an SEM image of a modified tetrapod-like zinc oxide nanoparticle-filled polypropylene composite fiber (diameter of about 2 microns, much larger than the nanoparticle size) prepared in example 3. As can be seen from fig. 1a and 1b, both fibers can be completely filamentized (which is beneficial to improving the overall mechanical properties), the fiber diameters are close, but the fiber filament diameters are more uniformly distributed without adding nanoparticles. In fig. 1b, there is no obvious exposure of the nanoparticles, which shows that the nanoparticles can be uniformly dispersed in the nanofibers, and promote the improvement of the tensile modulus of the composite fibers.
Comparative example 1
Under nitrogen atmosphere, the zinc foil is placed in a quartz tube (120 cm long and 10 cm in diameter) at 700 ℃ and oxygen and saturated water vapor are slowly introduced at a rate of 50 standard milliliters per minute to participate in the reaction (the volume ratio of the oxygen to the saturated water vapor is 1: 1, namely the introduction rates of the oxygen and the saturated water vapor are both 25 standard milliliters per minute), the oxygen flow rate and the reaction time are strictly controlled, and quadrangular pyramid-shaped zinc oxide nanoparticles with narrow size distribution range, average arm diameter within about 25nm and average arm length of about 70nm are obtained.
Dissolving 2.0g of coupling agent (gamma-aminopropyltriethoxysilane) in 50mL of water-ethanol solution, ultrasonically dispersing for 1h at room temperature, adding 0.8g of synthesized quadrangular pyramid zinc oxide nanoparticles, heating and stirring for 2h at 60 ℃, filtering, washing filter residues with deionized water, and then drying in vacuum at 60 ℃ to obtain the modified nano zinc oxide particles.
Dispersing polystyrene (Mw = 350000) in tetrahydrofuran, preparing a polystyrene solution with the mass concentration of 15%, then adding the modified nano zinc oxide particles obtained by the preparation method, and fully stirring to obtain an electrospinning solution; in the electrospinning solution, the mass concentration of the modified nano zinc oxide particles is 3%.
And (3) filling the electrospinning solution into an injector, spinning at a propelling speed of 0.02mL/min with the positive voltage set to be 20KV, and collecting the fibers on a rotating metal roller to prepare the modified quadrangular pyramid zinc oxide nanoparticle-filled polystyrene composite fibers or a fiber felt formed by randomly stacking a large number of fibers. A fiber mat (thickness controlled to be about 0.05 mm) having a size of 0.8cm × 3.0cm was cut out, the cross-sectional area was estimated from the mass thereof, and the tensile modulus thereof was measured in a dynamic mechanical analyzer (average of 10 effective measurements). The tensile modulus was increased by 139% compared to the control system without nanoparticles, which is different from the experimental system for preparing modified tetrapod-like zinc oxide nanoparticles-filled polystyrene composite fiber of comparative example 1 in that the modified tetrapod-like zinc oxide nanoparticles were not added to the electrospinning solution during the preparation process.
Comparative example 2
Under nitrogen atmosphere, the zinc foil is placed in a quartz tube (120 cm long and 10 cm in diameter) at 700 ℃ and oxygen and saturated water vapor are slowly introduced at a rate of 50 standard milliliters per minute to participate in the reaction (the volume ratio of the oxygen to the saturated water vapor is 1: 1, namely the introduction rates of the oxygen and the saturated water vapor are both 25 standard milliliters per minute), the oxygen flow rate and the reaction time are strictly controlled, and quadrangular pyramid-shaped zinc oxide nanoparticles with narrow size distribution range, average arm diameter within about 25nm and average arm length of about 70nm are obtained.
Dissolving 2.0g of coupling agent (gamma-aminopropyltriethoxysilane) in 50mL of water-ethanol solution, ultrasonically dispersing for 1h at room temperature, adding 0.8g of synthesized quadrangular pyramid zinc oxide nanoparticles, heating and stirring for 2h at 60 ℃, filtering, washing filter residues with deionized water, and then drying in vacuum at 60 ℃ to obtain the modified nano zinc oxide particles.
Dispersing polystyrene (Mw = 350000) in tetrahydrofuran, preparing a polystyrene solution with the mass concentration of 15%, then adding the modified nano zinc oxide particles obtained by the preparation method, and fully stirring to obtain an electrospinning solution; in the electrospinning solution, the mass concentration of the modified nano zinc oxide particles is 3.5%.
And (3) filling the electrospinning solution into an injector, spinning at a propelling speed of 0.02mL/min with the positive voltage set to be 30KV, and collecting the fibers on a rotating metal roller to prepare the modified quadrangular pyramid zinc oxide nanoparticle-filled polystyrene composite fibers or a fiber felt formed by randomly stacking a large number of fibers. A fiber mat (thickness controlled to be about 0.05 mm) having a size of 0.8cm × 3.0cm was cut out, the cross-sectional area was estimated from the mass thereof, and the tensile modulus thereof was measured in a dynamic mechanical analyzer (average of 10 effective measurements). The tensile modulus was increased 173% compared to the control system without nanoparticles, which is different from the experimental system for preparing modified tetrapyramid-like zinc oxide nanoparticle-filled polystyrene composite fiber of comparative example 2 in that the modified tetrapyramid-like zinc oxide nanoparticles were not added to the electrospinning solution during the preparation process.
Comparative example 1 the content of the modified nano zinc oxide particles was reduced compared to example 1, as shown in fig. 2a, which is a tensile curve of the composite fiber of example 1 with a nano particle content of 3.5wt%, and fig. 2b, which is a tensile curve of the composite fiber of comparative example 1 with a nano particle content of 3wt%, the tensile modulus decreased with the decrease of the nano particle content. Comparative example 2 compared to example 1, the fiber diameter was reduced (voltage was increased) and tensile testing showed that the diameter reduction resulted in a slight reduction in the tensile modulus of the nanofibers.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (5)
1. A preparation method of high tensile modulus polymer nano composite fiber based on electrostatic spinning technology is characterized by comprising the following steps:
1) preparing an electrospinning solution: dissolving a coupling agent in a water-ethanol mixed solution, performing ultrasonic dispersion for 1-3h at room temperature, adding quadrangular pyramid zinc oxide nano particles, heating and stirring for 0.5-4h, filtering, washing filter residues with deionized water, and performing vacuum drying to obtain modified nano zinc oxide particles; dispersing a polymer in an organic solvent to prepare a polymer solution, adding the modified nano zinc oxide particles prepared in the step (a) into the polymer solution, and fully stirring to obtain an electrospinning solution;
2) preparing high tensile modulus fiber: loading the electrospinning solution obtained in the step 1) into an injector, spinning at a propelling speed of 0.01-0.04mL/min, setting a positive voltage at 10-30kV, and collecting fibers obtained by spinning on a rotating metal roller or a rotating sheet to obtain the high-tensile-modulus polymer nano composite fibers;
in the step 1), the average arm diameter of the quadrangular pyramid zinc oxide nano particles is controlled within 50nm, and the average arm length is controlled within 100 nm;
in the step 1), the organic solvent is tetrahydrofuran or dimethylformamide.
2. The method for preparing the high-tensile-modulus polymer nano composite fiber based on the electrospinning technology according to claim 1, wherein in the step 1), the polymer is polystyrene, polyvinylidene fluoride, polylactic acid, polyimide, polyamide, polyvinyl alcohol, polyacrylonitrile or polypropylene.
3. The method for preparing the high tensile modulus polymer nanocomposite fiber based on the electrospinning technique according to claim 1, wherein in step 1), the coupling agent is a silane coupling agent or a titanate coupling agent;
the silane coupling agent is gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, vinyl triethoxysilane or vinyl tri (beta-methoxyethoxy) silane;
the titanate coupling agent is pyrophosphate titanate, isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate or isopropyl tri (dioctyl phosphate acyloxy) titanate.
4. The method for preparing the high-tensile-modulus polymer nanocomposite fiber based on the electrospinning technology according to claim 1, wherein the mass concentration of the polymer in the electrospinning solution in the step 1) is 5-30%.
5. The method for preparing the high-tensile-modulus polymer nanocomposite fiber based on the electrospinning technology according to claim 1, wherein the mass concentration of the modified nano zinc oxide particles in the electrospinning solution in the step 1) is 1-8%.
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| CN103694743A (en) * | 2013-11-27 | 2014-04-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Zinc oxide surface modification method by titanate coupling agent |
| CN107805887A (en) * | 2017-10-27 | 2018-03-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of electrostatic spinning supported catalyst air filting material and products thereof and application |
| CN108265345A (en) * | 2016-12-30 | 2018-07-10 | 香港理工大学 | A kind of synthetic fibers with air-cleaning function and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161705A (en) * | 2006-10-13 | 2008-04-16 | 中国科学院化学研究所 | Functional polymer nano composite material and preparation method and uses thereof |
| CN101358382A (en) * | 2008-08-26 | 2009-02-04 | 东华大学 | Antibacterial nano fiber material and preparation method thereof |
| CN101905974A (en) * | 2010-02-05 | 2010-12-08 | 西安理工大学 | Electrostatic spinning preparation method of ceramic nanometer composite fibers |
| CN103694743A (en) * | 2013-11-27 | 2014-04-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Zinc oxide surface modification method by titanate coupling agent |
| CN108265345A (en) * | 2016-12-30 | 2018-07-10 | 香港理工大学 | A kind of synthetic fibers with air-cleaning function and preparation method thereof |
| CN107805887A (en) * | 2017-10-27 | 2018-03-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of electrostatic spinning supported catalyst air filting material and products thereof and application |
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