CN109629032A - A kind of preparation method of the high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique - Google Patents
A kind of preparation method of the high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique Download PDFInfo
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- CN109629032A CN109629032A CN201811496271.5A CN201811496271A CN109629032A CN 109629032 A CN109629032 A CN 109629032A CN 201811496271 A CN201811496271 A CN 201811496271A CN 109629032 A CN109629032 A CN 109629032A
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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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- 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
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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
- D01F6/46—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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- 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
- D01F6/48—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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- 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
- D01F6/92—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
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Abstract
The invention belongs to electrostatic spinning technique fields, more particularly to the preparation method of the high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique, it is first using the quadrangle cone cell Zinc oxide nanoparticle of synthesis as raw material, the modified zinc-oxide nano branching particle in obtained surface is modified to nano particle using coupling agent, then it is sufficiently mixed the modified zinc-oxide nano branching particle in surface, polymer to obtain electrostatic spinning liquid in organic solvent, obtains the nano-composite fiber of high stretch modulus finally by electrostatic spinning.The present invention prepares high stretch modulus nanofiber by using electrospinning process, it, which is operated, is easy, is simple production process, low for equipment requirements, obtained nano-composite fiber only promotes the mechanical behavior of original polymer fiber and influences on other characteristics smaller, pulp freeness is big, stretch modulus is high, is easy to industrialize.
Description
Technical field
The invention belongs to electrostatic spinning technique fields, and in particular to a kind of high stretch modulus based on electrostatic spinning technique is poly-
Close the preparation method of object nano-composite fiber.
Background technique
Electrostatic spinning is a kind of method for efficiently preparing polymer nanometer composite fibers or fibrous felt materials, utilizes the skill
The functional material of art preparation has been widely used in bio-medical material, the multiple fields such as electronic device.Electrospun fibers diameter
About between 0.05 ~ 2 micron, it is not high to limit its application that lesser diameter typically results in mechanical stretch modulus.To electrostatic
It includes preparing superfine fibre (when diameter is less than certain size, such as that spinning fibre, which carries out the modified common methods of mechanics,
100nm, the growth of young's modulus and the reduction of diameter are inversely proportional), with stretch modulus bigger polymer or inorganic particulate into
It goes compound etc..It is more demanding to material, equipment and technique wherein to prepare superfine fibre, universality is bad, and by polymer and nothing
For the compound spinning strategy of machine particle because of easy to operate, reinforcing effect is obvious, is widely adopted at present, which may be implemented two
The high-quality complementation of kind substance, to greatly promote material property, especially mechanical property.Currently, compound in polymer nanocomposite
The spherical nanoparticle of a variety of materials, nanometer rods, nanotube, nanometer sheet are generallyd use in the electrostatic spinning preparation process of fiber
Deng, however the easy reunion of these particles, its dispersion and arrangement in solvent or polymeric matrix is influenced, so as to cause final
Mechanics reinforcing effect is limited.In addition, also there is relevant research to carry out nano particle, surface is modified to add polymeric system,
Promote the dispersion of particle and enhances its interface binding power between polymer.In order to reach the reinforcing effect of target, using this
The polymer nanometer composite fibers of method preparation still have the excessively high problem of loading, and to the processing requirement of nano particle compared with
It is high.And the nano particle of three-dimensional branching (such as quadrangular pyramid) will be answered due to the intrinsic advantage in spatial dispersion in enhancing polymer nanocomposite
Condensating fiber field shows very big potentiality.
Summary of the invention
It is insufficient for the above-mentioned prior art, that it is an object of that present invention to provide a kind of operations is easy, low for equipment requirements, compared with
The preparation method of the high stretch modulus polymer nanometer composite fibers based on electrostatic spinning can be obtained in the case of low additive amount.
A kind of preparation method of the high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique, feature exist
In including the following steps:
1) it configures Electrospun solution: coupling agent being dissolved in water-ethanol mixed solution, is added four after ultrasonic disperse 1-3h at room temperature
Pyramidal Zinc oxide nanoparticle filters after heating stirring 0.5-4h, and filter residue is washed with deionized, and changes to obtain the final product after vacuum drying
Nano granular of zinc oxide after property；In organic solvent by polymer dispersion, preparation forms polymer solution, is prepared into above-mentioned
To modified nano granular of zinc oxide be added in the polymer solution, Electrospun solution is obtained after being sufficiently stirred；
2) high tensile modulus fibers are prepared: Electrospun solution obtained by step 1) being encased in syringe, then in 0.01-
Spinning under the fltting speed of 0.04mL/min, positive voltage are set as 10-30KV, and the fiber that spinning obtains collects the metal in rotation
On roller or thin slice, the high stretch modulus polymer nanometer composite fibers are obtained.
A kind of preparation method of the high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique,
Be characterized in that in step 1), polymer be polystyrene, Kynoar, polylactic acid, polyimides, polyamide, polyvinyl alcohol,
Polyacrylonitrile or polypropylene.
A kind of preparation method of the high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique,
It is characterized in that in step 1), the coupling agent is silane coupling agent or titanate coupling agent；
Silane coupling agent is γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, vinyl
Triethoxysilane or vinyl three (beta-methoxy ethyoxyl) silane；
Titanate coupling agent be pyrophosphate titanate esters, two oleic acid acyloxy of isopropyl (dioctyl phosphoric acid acyloxy) titanate esters or
Isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters.
A kind of preparation method of the high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique,
It is characterized in that in step 1), the average arm diameter control of quadrangle cone cell Zinc oxide nanoparticle is within 50nm, average arm length control
System is within 100nm.
A kind of preparation method of the high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique,
It is characterized in that in step 1), organic solvent is tetrahydrofuran or dimethylformamide.
A kind of preparation method of the high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique,
It is characterized in that in step 1) Electrospun solution, the mass concentration of polymer is 5 ~ 30%.
A kind of preparation method of the high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique,
It is characterized in that in step 1) Electrospun solution, the mass concentration of modified nano granular of zinc oxide is 1 ~ 8%.
By using above-mentioned technology, compared with prior art, the invention has the following beneficial effects:
The present invention prepares high stretch modulus polymer nanometer composite fibers by using the method for electrostatic spinning, operation is easy,
Simple production process, low for equipment requirements, obtained polymer nanometer composite fibers Young's modulus height, nano particle loading
It is small, it is easy to industrialize.
After the present invention is modified nano granular of zinc oxide using coupling agent, coupling agent molecule chain on nano particle with
Polymer chain is intertwine with each other, so that the interaction force between nano particle and polymers compositions is remarkably reinforced, is conducive to nanometer
Stress transfer under the dispersion and stress condition of particle between nano particle and polymeric acceptor phase, and finally enhance polymer nanocomposite
The stretch modulus of composite fibre.
Detailed description of the invention
Fig. 1 a is the scanning electron microscope (SEM) photograph of the polypropylene composite materials fiber of 3 control systems of embodiment；
Fig. 1 b is the scanning electron microscope (SEM) photograph of the polypropylene composite materials fiber of 3 experimental system of embodiment；
Fig. 2 a is the extension test stress-strain diagram of the polystyrene composite fibre of 1 experimental system of embodiment；
Fig. 2 b is the extension test stress-strain diagram of the polystyrene composite fibre of 1 experimental system of comparative example.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
Embodiment 1
In a nitrogen environment, zinc foil is placed in 700 DEG C of quartz ampoule (120 centimeter lengths, 10 centimetres of diameter) and with 50 standards milli
Liter/min rate be slowly introducing oxygen and saturated steam make its participate in reaction (oxygen and saturated steam volume ratio 1:1,
That is the rate that is passed through of oxygen and saturated steam is 25 standard milliliters/minute), strict control oxygen gas flow rate and reaction time are simultaneously
It is narrow to obtain size distribution ranges, within average arm diameter about 25nm, the quadrangle cone cell zinc-oxide nano of average arm length about 70nm
Grain.
The coupling agent (γ-aminopropyl triethoxysilane) of 2.0g is dissolved in 50mL water-ethanol mixed solution (water and second
Alcohol volume ratio is 1:1) in, the quadrangle cone cell Zinc oxide nanoparticle of the above-mentioned synthesis of 0.8g is added after ultrasonic disperse 1h at room temperature,
It is filtered after heating stirring 2h at 60 DEG C, filter residue is washed with deionized, then to obtain the final product modified after vacuum drying at 60 DEG C
Nano granular of zinc oxide.
Polystyrene (Mw=350000) is dispersed in tetrahydrofuran, it is molten to prepare the polystyrene that mass concentration is 15%
Liquid is then added the above-mentioned modified nano granular of zinc oxide being prepared, Electrospun solution is obtained after being sufficiently stirred；In electricity
In spinning solution, the mass concentration of modified nano granular of zinc oxide is 3.5%.
Electrospun solution is fitted into syringe, then the spinning under the fltting speed of 0.02mL/min, positive voltage setting
For 20KV, fiber is collected on the metal roller of rotation, and the polyphenyl second of modified quadrangle cone cell Zinc oxide nanoparticle filling is made
Alkene composite fibre or a large amount of fibers randomly stack the fibrofelt of formation.It is (thick to cut out the fibrofelt having a size of 0.8cm × 3.0cm
Degree control is in 0.05mm or so), according to its quality estimation sectional area, then uses in dynamic mechanical analyzer and measure its stretching die
It measures (average value for taking 10 effective measurement results).Stretch modulus compares the control systems increase by 181% for being not added with nano particle,
Control systems and embodiment 1 herein prepare the polystyrene composite fibre of modified quadrangle cone cell Zinc oxide nanoparticle filling
Experimental system is compared, the difference is that being not added with modified quadrangle cone cell zinc-oxide nano in the Electrospun solution of preparation process
Grain.The reason of the present embodiment addition nano particle post-tensioning modulus obviously increases is as follows: nano particle is owned to compare polymer
Considerably higher Young's modulus；It is largely stronger short with polymer affinity interaction by having on the nano particle after coupling agent modified
Chain, and intertwine with each other with polymer chain, improve the interaction force between polymer and nano particle；In addition, modified
Particle can spread more evenly across in the polymer；Under tension, stress is transmitted to nano particle from polymer and makes multiple
The stretch modulus of condensating fiber significantly improves.
Embodiment 2
In a nitrogen environment, zinc foil is placed in 700 DEG C of quartz ampoule (120 centimeter lengths, 10 centimetres of diameter) and with 50 standards milli
Liter/min rate be slowly introducing oxygen and saturated steam make its participate in reaction (oxygen and saturated steam volume ratio 1:1,
That is the rate that is passed through of oxygen and saturated steam is 25 standard milliliters/minute), strict control oxygen gas flow rate and reaction time are simultaneously
It is narrow to obtain size distribution ranges, within average arm diameter about 25nm, the quadrangle cone cell zinc-oxide nano of average arm length about 70nm
Grain.
By the coupling agent (pyrophosphate titanate esters) of 2.0g be dissolved in 50mL water-ethanol solution (water and ethyl alcohol volume ratio are 1:
1) in, the quadrangle cone cell Zinc oxide nanoparticle of the above-mentioned synthesis of 0.8g is added after ultrasonic disperse 1h at room temperature, is heated at 60 DEG C
Filtered after stirring 2h, filter residue is washed with deionized, then at 60 DEG C after vacuum drying up to modified nano zine oxide
Particle.
Kynoar (Mw=250000) is dispersed in tetrahydrofuran, the Kynoar that mass concentration is 15% is prepared
Solution is then added the above-mentioned modified nano granular of zinc oxide being prepared, Electrospun solution is obtained after being sufficiently stirred；?
In Electrospun solution, the mass concentration of modified nano granular of zinc oxide is 3.5%.
Electrospun solution is fitted into syringe, then the spinning under the fltting speed of 0.02mL/min, positive voltage setting
For 20KV, fiber is collected on the metal roller of rotation, and the poly- inclined fluorine of modified quadrangle cone cell Zinc oxide nanoparticle filling is made
Ethylene composite fibre or a large amount of fibers randomly stack the fibrofelt of formation.Cut out the fibrofelt having a size of 0.8cm × 3.0cm
Then (thickness control is in 0.05mm or so) is used in dynamic mechanical analyzer according to its quality estimation sectional area and is measured its drawing
Stretch modulus (average value for taking 10 effective measurement results).Stretch modulus compares the control systems increase for being not added with nano particle
161%, the Kynoar that control systems and embodiment 2 herein prepare modified quadrangle cone cell Zinc oxide nanoparticle filling is multiple
The experimental system of condensating fiber is compared, the difference is that being not added with modified quadrangle cone cell oxidation in the Electrospun solution of preparation process
Zinc nanoparticles.
Embodiment 3
In a nitrogen environment, zinc foil is placed in 700 DEG C of quartz ampoule (120 centimeter lengths, 10 centimetres of diameter) and with 50 standards milli
Liter/min rate be slowly introducing oxygen and saturated steam make its participate in reaction (oxygen and saturated steam volume ratio 1:1,
That is the rate that is passed through of oxygen and saturated steam is 25 standard milliliters/minute), strict control oxygen gas flow rate and reaction time are simultaneously
It is narrow to obtain size distribution ranges, within average arm diameter about 25nm, the quadrangle cone cell zinc-oxide nano of average arm length about 70nm
Grain.
The coupling agent (γ-aminopropyl triethoxysilane) of 2.0g is dissolved in 50mL water-ethanol solution, is surpassed at room temperature
The quadrangle cone cell Zinc oxide nanoparticle that 0.8g is synthesized is added after dispersing 1h in sound, filters after heating stirring 2h at 60 DEG C, filter residue
Be washed with deionized, then at 60 DEG C after vacuum drying up to modified nano granular of zinc oxide.
Polypropylene (Mw=350000) is dispersed in tetrahydrofuran, the polypropylene solution that mass concentration is 15% is prepared, with
The above-mentioned modified nano granular of zinc oxide being prepared is added afterwards, Electrospun solution is obtained after being sufficiently stirred；In Electrospun
In solution, the mass concentration of modified nano granular of zinc oxide is 3.5%.
Electrospun solution is fitted into syringe, then the spinning under the fltting speed of 0.02mL/min, positive voltage setting
For 20KV, fiber is collected on the metal roller of rotation, and the polypropylene of modified quadrangle cone cell Zinc oxide nanoparticle filling is made
Composite fibre or a large amount of fibers randomly stack the fibrofelt of formation.Cut out the fibrofelt (thickness having a size of 0.8cm × 3.0cm
Control is in 0.05mm or so), according to its quality estimation sectional area, then uses in dynamic mechanical analyzer and measure its stretch modulus
(average value for taking 10 effective measurement results).Stretch modulus compares the control systems increase by 172% for being not added with nano particle, this
The control systems and embodiment 3 at place prepare the experiment of the polypropylene composite materials fiber of modified quadrangle cone cell Zinc oxide nanoparticle filling
System is compared, the difference is that being not added with modified quadrangle cone cell Zinc oxide nanoparticle in the Electrospun solution of preparation process.
Embodiment 4
In a nitrogen environment, zinc foil is placed in 700 DEG C of quartz ampoule (120 centimeter lengths, 10 centimetres of diameter) and with 50 standards milli
Liter/min rate be slowly introducing oxygen and saturated steam make its participate in reaction (oxygen and saturated steam volume ratio 1:1,
That is the rate that is passed through of oxygen and saturated steam is 25 standard milliliters/minute), strict control oxygen gas flow rate and reaction time are simultaneously
It is narrow to obtain size distribution ranges, within average arm diameter about 25nm, the quadrangle cone cell zinc-oxide nano of average arm length about 70nm
Grain.
The coupling agent (γ-aminopropyl triethoxysilane) of 2.0g is dissolved in 50mL water-ethanol solution, is surpassed at room temperature
The quadrangle cone cell Zinc oxide nanoparticle that 0.8g is synthesized is added after dispersing 1h in sound, filters after heating stirring 2h at 60 DEG C, filter residue
Be washed with deionized, then at 60 DEG C after vacuum drying up to modified nano granular of zinc oxide.
Polylactic acid (Mw=250000) is dispersed in tetrahydrofuran, the PLA solution that mass concentration is 15% is prepared, with
The above-mentioned modified nano granular of zinc oxide being prepared is added afterwards, Electrospun solution is obtained after being sufficiently stirred；In Electrospun
In solution, the mass concentration of modified nano granular of zinc oxide is 3.5%.
Electrospun solution is fitted into syringe, then the spinning under the fltting speed of 0.02mL/min, positive voltage setting
For 20KV, fiber is collected on the metal roller of rotation, and the polylactic acid of modified quadrangle cone cell Zinc oxide nanoparticle filling is made
Composite fibre or a large amount of fibers randomly stack the fibrofelt of formation.Cut out the fibrofelt (thickness having a size of 0.8cm × 3.0cm
Control is in 0.05mm or so), according to its quality estimation sectional area, then uses in dynamic mechanical analyzer and measure its stretch modulus
(average value for taking 10 effective measurement results).Stretch modulus compares the control systems increase by 129% for being not added with nano particle, this
The control systems and embodiment 4 at place prepare the experiment of the PLA Composite Fiber of modified quadrangle cone cell Zinc oxide nanoparticle filling
System is compared, the difference is that being not added with modified quadrangle cone cell Zinc oxide nanoparticle in the Electrospun solution of preparation process.
In embodiment 1 ~ 4, polymeric matrix material is different, also not identical to the promotion degree of stretch modulus.Fig. 1 a is real
The SEM figure of the control systems (polypropylene fibre without nano particle) of the preparation of example 3 is applied, Fig. 1 b is modification prepared by embodiment 3
(2 microns of diameter are much larger than nanometer to the SEM figure of the polypropylene composite materials fiber of quadrangle cone cell Zinc oxide nanoparticle filling
Particle size).Can be seen that two kinds of fibers with Fig. 1 b according to fig. 1a completely (can be conducive to promote whole mechanical property at silk
Can), fibre diameter is close, but filament diameter is more uniformly spread when not adding nano particle.It is not received significantly in Fig. 1 b
The exposed situation of rice grain illustrates that nano particle can be evenly dispersed in nanofiber, stretches modulus to composite fibre and mentions
Rising has facilitation.
Comparative example 1
In a nitrogen environment, zinc foil is placed in 700 DEG C of quartz ampoule (120 centimeter lengths, 10 centimetres of diameter) and with 50 standards milli
Liter/min rate be slowly introducing oxygen and saturated steam make its participate in reaction (oxygen and saturated steam volume ratio 1:1,
That is the rate that is passed through of oxygen and saturated steam is 25 standard milliliters/minute), strict control oxygen gas flow rate and reaction time are simultaneously
It is narrow to obtain size distribution ranges, within average arm diameter about 25nm, the quadrangle cone cell zinc-oxide nano of average arm length about 70nm
Grain.
The coupling agent (γ-aminopropyl triethoxysilane) of 2.0g is dissolved in 50mL water-ethanol solution, is surpassed at room temperature
The quadrangle cone cell Zinc oxide nanoparticle that 0.8g is synthesized is added after dispersing 1h in sound, filters after heating stirring 2h at 60 DEG C, filter residue
Be washed with deionized, then at 60 DEG C after vacuum drying up to modified nano granular of zinc oxide.
Polystyrene (Mw=350000) is dispersed in tetrahydrofuran, it is molten to prepare the polystyrene that mass concentration is 15%
Liquid is then added the above-mentioned modified nano granular of zinc oxide being prepared, Electrospun solution is obtained after being sufficiently stirred；In electricity
In spinning solution, the mass concentration of modified nano granular of zinc oxide is 3%.
Electrospun solution is fitted into syringe, then the spinning under the fltting speed of 0.02mL/min, positive voltage setting
For 20KV, fiber is collected on the metal roller of rotation, and the polyphenyl second of modified quadrangle cone cell Zinc oxide nanoparticle filling is made
Alkene composite fibre or a large amount of fibers randomly stack the fibrofelt of formation.It is (thick to cut out the fibrofelt having a size of 0.8cm × 3.0cm
Degree control is in 0.05mm or so), according to its quality estimation sectional area, then uses in dynamic mechanical analyzer and measure its stretching die
It measures (average value for taking 10 effective measurement results).Stretch modulus compares the control systems increase by 139% for being not added with nano particle,
Control systems and comparative example 1 herein prepare the polystyrene composite fibre of modified quadrangle cone cell Zinc oxide nanoparticle filling
Experimental system is compared, the difference is that being not added with modified quadrangle cone cell zinc-oxide nano in the Electrospun solution of preparation process
Grain.
Comparative example 2
In a nitrogen environment, zinc foil is placed in 700 DEG C of quartz ampoule (120 centimeter lengths, 10 centimetres of diameter) and with 50 standards milli
Liter/min rate be slowly introducing oxygen and saturated steam make its participate in reaction (oxygen and saturated steam volume ratio 1:1,
That is the rate that is passed through of oxygen and saturated steam is 25 standard milliliters/minute), strict control oxygen gas flow rate and reaction time are simultaneously
It is narrow to obtain size distribution ranges, within average arm diameter about 25nm, the quadrangle cone cell zinc-oxide nano of average arm length about 70nm
Grain.
The coupling agent (γ-aminopropyl triethoxysilane) of 2.0g is dissolved in 50mL water-ethanol solution, is surpassed at room temperature
The quadrangle cone cell Zinc oxide nanoparticle that 0.8g is synthesized is added after dispersing 1h in sound, filters after heating stirring 2h at 60 DEG C, filter residue
Be washed with deionized, then at 60 DEG C after vacuum drying up to modified nano granular of zinc oxide.
Polystyrene (Mw=350000) is dispersed in tetrahydrofuran, it is molten to prepare the polystyrene that mass concentration is 15%
Liquid is then added the above-mentioned modified nano granular of zinc oxide being prepared, Electrospun solution is obtained after being sufficiently stirred；In electricity
In spinning solution, the mass concentration of modified nano granular of zinc oxide is 3.5%.
Electrospun solution is fitted into syringe, then the spinning under the fltting speed of 0.02mL/min, positive voltage setting
For 30KV, fiber is collected on the metal roller of rotation, and the polyphenyl second of modified quadrangle cone cell Zinc oxide nanoparticle filling is made
Alkene composite fibre or a large amount of fibers randomly stack the fibrofelt of formation.It is (thick to cut out the fibrofelt having a size of 0.8cm × 3.0cm
Degree control is in 0.05mm or so), according to its quality estimation sectional area, then uses in dynamic mechanical analyzer and measure its stretching die
It measures (average value for taking 10 effective measurement results).Stretch modulus compares the control systems increase by 173% for being not added with nano particle,
Control systems and comparative example 2 herein prepare the polystyrene composite fibre of modified quadrangle cone cell Zinc oxide nanoparticle filling
Experimental system is compared, the difference is that being not added with modified quadrangle cone cell zinc-oxide nano in the Electrospun solution of preparation process
Grain.
Comparative example 1 compared with Example 1, reduces the content of modified nano granular of zinc oxide, if Fig. 2 a is nanometer
The stress strain curve of 1 composite fibre of embodiment when granule content 3.5wt%, the comparative example 1 when Fig. 2 b is nano-particle content 3wt%
The stress strain curve of composite fibre, stretch modulus decline with the reduction of nano-particle content.Comparative example 2 compared with Example 1,
Fibre diameter (increasing voltage) is reduced, extension test is shown, diameter reduces so that the stretch modulus of nanofiber is slightly reduced.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated.
Claims (7)
1. a kind of preparation method of the high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique, it is characterised in that
Include the following steps:
1) it configures Electrospun solution: coupling agent being dissolved in water-ethanol mixed solution, is added four after ultrasonic disperse 1-3h at room temperature
Pyramidal Zinc oxide nanoparticle filters after heating stirring 0.5-4h, and filter residue is washed with deionized, and changes to obtain the final product after vacuum drying
Nano granular of zinc oxide after property；In organic solvent by polymer dispersion, preparation forms polymer solution, is prepared into above-mentioned
To modified nano granular of zinc oxide be added in the polymer solution, Electrospun solution is obtained after being sufficiently stirred；
2) high tensile modulus fibers are prepared: Electrospun solution obtained by step 1) being encased in syringe, then in 0.01-
Spinning under the fltting speed of 0.04mL/min, positive voltage are set as 10-30KV, and the fiber that spinning obtains collects the metal in rotation
On roller or thin slice, the high stretch modulus polymer nanometer composite fibers are obtained.
2. a kind of high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique according to claim 1
Preparation method, it is characterised in that in step 1), polymer is polystyrene, Kynoar, polylactic acid, polyimides, polyamides
Amine, polyvinyl alcohol, polyacrylonitrile or polypropylene.
3. a kind of high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique according to claim 1
Preparation method, it is characterised in that in step 1), the coupling agent is silane coupling agent or titanate coupling agent；
Silane coupling agent is γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, vinyl
Triethoxysilane or vinyl three (beta-methoxy ethyoxyl) silane；
Titanate coupling agent be pyrophosphate titanate esters, two oleic acid acyloxy of isopropyl (dioctyl phosphoric acid acyloxy) titanate esters or
Isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters.
4. a kind of high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique according to claim 1
Preparation method, it is characterised in that in step 1), the average arm diameter control of quadrangle cone cell Zinc oxide nanoparticle within 50nm,
Average arm length controls within 100nm.
5. a kind of high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique according to claim 1
Preparation method, it is characterised in that in step 1), organic solvent is tetrahydrofuran or dimethylformamide.
6. a kind of high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique according to claim 1
Preparation method, it is characterised in that in step 1) Electrospun solution, the mass concentration of polymer is 5 ~ 30%.
7. a kind of high stretch modulus polymer nanometer composite fibers based on electrostatic spinning technique according to claim 1
Preparation method, it is characterised in that in step 1) Electrospun solution, the mass concentration of modified nano granular of zinc oxide is 1 ~ 8%.
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